WO2010103065A1 - Fungicidal compositions and their use - Google Patents

Fungicidal compositions and their use Download PDF

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Publication number
WO2010103065A1
WO2010103065A1 PCT/EP2010/053089 EP2010053089W WO2010103065A1 WO 2010103065 A1 WO2010103065 A1 WO 2010103065A1 EP 2010053089 W EP2010053089 W EP 2010053089W WO 2010103065 A1 WO2010103065 A1 WO 2010103065A1
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compound
methyl
alkyl
formula
phenyl
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PCT/EP2010/053089
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French (fr)
Inventor
Jens Renner
Marianna Vrettou-Schultes
Jochen Dietz
Sarah Ulmschneider
Egon Haden
Silke Schäfer
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Basf Se
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Publication of WO2010103065A1 publication Critical patent/WO2010103065A1/en

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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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • 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

  • the present invention relates to compositions of fungicidally active compounds comprising at least one substituted pyrrole compound of formula I as defined below and at least one further fungicidally active compound II.
  • the invention furthermore relates to a method for controlling harmful fungi, wherein the fungi, their habitat or the materials or plants to be protected against fungal attack, or the soil or propagation material are treated with an effective amount of at least one substituted pyrrole compound of formula I in combination with at least one compound Il or with an effective amount of a composition according to the invention, to a method for protection of seed, comprising contacting the seeds with at least one compound of formula I in combination with at least one compound II, and to the use of the composition according to the invention for controlling harmful fungi.
  • a further problem arising with the use of fungicides is that the repeated and exclusive application of an individual fungicidal compound often leads to a rapid selection of harmful fungi which have developed natural or adapted resistance against the active compound in question. Normally, such fungi strains are also cross-resistant against other active ingredients having the same mode of action. An effective control of the pathogens with said active compounds is then not possible anymore. However, active ingredients having new mechanisms of action are difficult and expensive to develop.
  • plant health comprises various sorts of improvements of plants that are not connected to the control of fungi.
  • advantageous properties are improved crop characteristics including: emergence, crop yields, protein content, oil content, starch content, more developed root system (improved root growth), improved stress tolerance (e.g.
  • tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, enhanced plant vigor, increased plant stand and early and better germination; or any other advantages familiar to a person skilled in the art.
  • composition containing a compound of formula I as defined hereinafter and a compound Il as defined hereinafter show markedly enhanced action against fungi compared to the control rates that are possible with the individual compounds and/or is suitable for improving the health of plants when applied to plants, parts of plants, seeds, or at their locus of growth.
  • compositions of the invention goes far beyond the fungicidal and/or plant health improving action of the active compounds present in the mixture alone.
  • compositions of fungicidally active ingredients comprising, as active components,
  • R 1 and R 3 independently of each other, are hydrogen, d-C ⁇ -alkyl which may carry 1 , 2, 3 or 4 substituents R 7 , d-C ⁇ -haloalkyl, C2-C6-alkenyl which may carry 1 , 2, 3 or 4 substituents R 7 , C2-C6-haloalkenyl, C2-C6-alkynyl which may carry 1 , 2, 3 or 4 substituents R 7 , C2-C6-haloalkynyl, Cs-C ⁇ -cycloalkyl which may carry 1 , 2, 3 or 4 substituents R 8 , Cs-C ⁇ -cycloalkenyl which may carry 1 , 2, 3 or 4 substituents R 8 , tri-(Ci-C 4 -alkyl)-silyl, aryl, aryl-Ci-C 4 -alkyl, aryloxy-Ci-C 4 -alkyl, arylthio-Ci-C 4 -
  • R 2 is Ci-C ⁇ -alkyl which may carry 1 , 2, 3 or 4 substituents R 7 , Ci-C ⁇ -haloalkyl, C2-C6-alkenyl which may carry 1 , 2, 3 or 4 substituents R 7 , C2-C6- haloalkenyl, C2-C6-alkynyl which may carry 1 , 2, 3 or 4 substituents R 7 , C2-C6-haloalkynyl, Cs-C ⁇ -cycloalkyl which may carry 1 , 2, 3 or 4 substituents R 8 , Cs-C ⁇ -cycloalkenyl which may carry 1 , 2, 3 or 4 substituents R 8 , aryl, aryl-Ci-C 4 -alkyl, or a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO
  • R 5 and R 6 are, independently of each other, hydrogen, halogen, cyano, Ci-C ⁇ - alkyl which may carry 1 , 2, 3 or 4 substituents R 7 , d-C ⁇ -haloalkyl, C2-C6- alkenyl which may carry 1 , 2, 3 or 4 substituents R 7 , C2-C6-haloalkenyl, C2-C6-alkynyl which may carry 1 , 2, 3 or 4 substituents R 7 , C2-C6- haloalkynyl, Cs-C ⁇ -cycloalkyl which may carry 1 , 2, 3 or 4 substituents R 8 , C3-C6-cycloalkenyl which may carry 1 , 2, 3 or 4 substituents R 8 , Ci-C ⁇ - alkoxy whose alkyl moiety may carry 1 , 2, 3 or 4 substituents R 7 , C-i-C ⁇ - haloalkoxy, d-C ⁇ -alkylthio whose al
  • Ci-C4-haloalkyl Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro;
  • R 7 is hydroxyl, cyano, nitro, Cs-C ⁇ -cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C 4 -alkylthio, Ci-C 4 -haloalkylthio, Ci-C 4 -alkylcarbonyl, Ci-C 4 - alkoxycarbonyl, tri-(Ci-C4-alkyl)-silyl, aryl and a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the two last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C
  • R 8 is halogen, hydroxyl, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, tri-(Ci-C4-alkyl)-silyl, aryl and a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the
  • Ci-C4-alkoxy Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro;
  • A) azoles selected from the group consisting of
  • - 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:
  • B) strobilurins selected from the group consisting of 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
  • - carboxanilides benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4-methyl- thiazole-5-carboxanilide, 2-chloro-N-(1 ,1 ,3-trimethyl-indan-4-yl)-nicotinamide,
  • - benzoic acid amides flumetover, fluopicolide, fluopyram, zoxamide, N-(3-Ethyl- 3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide;
  • carpropamid carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthiofarm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide;
  • - 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-trichloro- pyridine-2,6-di-carbonitrile, N-(1 -(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4- 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;
  • 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
  • - thio- and dithiocarbamates ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram; - carbamates: benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamocarb hydrochloric!, valiphenal and N-(1-(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester; and F) other active compounds, selected from the group consisting of
  • guanidine 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,
  • 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;
  • the invention also relates to a method for controlling harmful, preferably phytopathogenic fungi, wherein the fungi, their habitat or the materials or plants to be protected against fungal attack, or the soil or propagation material are treated with an effective amount of at least compound of formula I in combination with at least one compound II, where the compounds I and Il are as defined above or below, or with an effective amount of a composition according to the invention.
  • the invention furthermore relates to a method for protection of seed, comprising contacting the seeds with at least one compound of formula I in combination with at least one compound II, where the compounds I and Il are as defined above or below, in fungicidally effective amounts or with an effective amount of a composition according to the invention.
  • the invention also relates to the use of the composition according to the invention for controlling harmful fungi, preferably phytopathogenic fungi.
  • the present invention further relates to plant-protecting active ingredient compositions having synergistically enhanced action of improving the health of plants and to a method of applying such compositions of the invention to the plants.
  • composition according to the invention may be a physical mixture of the at least one compound I and the at least one compound II. Accordingly, the invention also provides a mixture comprising at least one compound I and at least one compound II. However, the composition may also be any combination of at least one compound I with at least one compound II, it not being required for compounds I and Il to be present together in the same formulation.
  • kits 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 two-component kit is a two-component kit.
  • the present invention also relates to a two-component kit, comprising a first component which in turn comprises at least one compound I, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary, and a second component which in turn comprises at least one compound II, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary.
  • a first component which in turn comprises at least one compound I, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary
  • a second component which in turn comprises at least one compound II, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary.
  • Suitable liquid and solid carriers, surfactants and customary auxiliaries are described below.
  • the “combined" use of at least one compound I with and at least one compound Il or the treatment according to the invention with the at least one compound I "in combination with” at least one compound Il on the one hand can be understood as using a physical mixture of at least one compound I and at least one compound II.
  • the combined use may also consist in using the at least one compound I and the at least one compound Il separately, but within a sufficiently short time of one another so that the desired effect can take place. More detailed illustrations of the combined use can be found in the specifications below.
  • the term "plant” refers to an entire plant, a part of the plant or the propagation material of the plant, that is, the seed or the seedling.
  • 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.
  • vegetative plant material such as cuttings and tubers (e. g. potatoes)
  • These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • Locus means a plant, seed, soil, area, material or environment in which a pest is growing or may grow.
  • Agriculturally acceptable salt means a salt the cation of which is known and accepted in the art for the formation of salts for agricultural or horticultural use. Suitable agriculturally acceptable salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention.
  • the salts are water-soluble. They can be formed in a customary method, e.g. by reacting the active compound with an acid of the anion in question if the active compound has a basic functionality or by reacting an acidic active compound with a suitable base.
  • Said acid addition salts are, for example, formed with mineral acids, typically sulfuric acid, nitric acid, a phosphoric acid or a hydrogen halide, such as hydrochloric acid or hydrobromic acid, with organic carboxylic acids, typically acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, with hydroxycarboxylic acids, typically ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with organic sulfonic acids, typically methanesulfonic acid or p-toluenesulfonic acid.
  • mineral acids typically sulfuric acid, nitric acid, a phosphoric acid or a hydrogen halide, such as hydrochloric acid or hydrobromic acid
  • organic carboxylic acids typically acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid
  • hydroxycarboxylic acids typically as
  • the compounds of formula I can also form salts with bases.
  • Suitable salts with bases are, for example, metal salts, typically alkali metal salts; or alkaline earth metal salts, e.g. sodium salts, potassium salts or magnesium salts, or salts with ammonia or an organic amine, e.g. morpholine, piperidine, pyrrolidine, a mono-, di- or trialkylamine, typically ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or trihydroxyalkylamine, typically mono-, di- or triethanolamine.
  • the formation of corresponding internal salts is also possible.
  • the compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
  • C n -Cm indicates the number of carbon atoms of an individual substituent or the respective part of a substituent.
  • Halo or halogen, as used herein, refers to Cl, Br, I or F.
  • Cyano as used herein refers to a CN group.
  • Alkyl refers to a saturated hydrocarbon radical which may be straight- chain or branched-chain (for example, ethyl, isopropyl, t-amyl, or hexyl) and contains from 1 to 6, in particular 1 to 4 carbon atoms. This definition applies both when the term is used alone and when it is used as part of a compound term, such as "haloalkyl", “alkoxy”, “alkoxyalkyl”, “alkylthio” and similar terms. In some embodiments, preferred alkyl groups are those containing 1 to 4 carbon atoms. Ci-C4-alkyl is a linear or branched saturated hydrocarbon radical having 1 to 4 carbon atoms.
  • d-C ⁇ -alkyl is a linear or branched saturated hydrocarbon radical having 1 to 6 carbon atoms. Examples are, apart those mentioned above for Ci-C4-alkyl, pentyl, hexyl and the positional isomers thereof.
  • Alkylene refers to a bivalent saturated hydrocarbon radical which is straight-chain. Alkylene is unsubstituted or may carry a substituent selected from Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and cyano.
  • alkylene include, but are not limited to methylene (CHb), 1 ,1-ethandiyl, 1 ,2-ethandiyl, 1 ,1-propandiyl, 1 ,2-propandiyl, 1 ,3-propandiyl, 1 ,1-butandiyl, 1 ,2-butandiyl, 1 ,3-butandiyl, 2,3-butandiyl or 1 ,4-butandiyl.
  • CHb methylene
  • alkylene include, but are not limited to methylene (CHb), 1 ,1-ethandiyl, 1 ,2-ethandiyl, 1 ,1-propandiyl, 1 ,2-propandiyl, 1 ,3-propandiyl, 1 ,1-butandiyl, 1 ,2-butandiyl, 1 ,3-butandiyl, 2,3-butandiyl or 1 ,4-butandi
  • Haloalkyl refers to alkyl, as defined herein, wherein the hydrogen atoms are partly or completely replaced by halogen atoms, in particular fluorine or chlorine atoms.
  • Representative examples of Ci-C ⁇ - and Ci-C4-haloalkyl include, but are not limited to, chloromethyl, 2-fluoroethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like. This definition applies both when the term is used alone and when it is used as part of a compound term, such as "haloalkyloxy", “haloalkylthio" and similar terms.
  • preferred haloalkyl groups are those containing 1 or 2 carbon atoms.
  • Alkenyl refers to a straight or branched chain hydrocarbon containing from 2 to 6 carbons and containing at least one carbon-carbon double bond formed by the removal of two hydrogens.
  • Representative examples of C2-C6-alkenyl include, but are not limited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, and the like.
  • “Lower alkenyl” as used herein, is a subset of alkenyl and refers to a straight or branched chain hydrocarbon group containing from 2 to 4 carbon atoms.
  • Representative examples of C2-C4-alkenyl include, but are not limited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, and 3-butenyl.
  • Haloalkenyl as used herein, which is also expressed as “alkenyl which is partially or fully halogenated”, refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 ("C2-C 4 -haloalkenyl") or 2 to 6 (“C 2 -C 6 -haloalkenyl”) carbon atoms and a double bond in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.
  • Alkynyl refers to a straight or branched chain hydrocarbon group containing from 2 to 6 carbon atoms and containing at least one carbon-carbon triple bond.
  • Representative examples of C2-C6-alkynyl include, but are not limited, to ethynyl, 1-propynyl, 2-propynyl, 3-butynyl, 1-butynyl, 1-pentynyl, 2-pentynyl, 1-hexynyl, 2-hexynyl and the like.
  • “Lower alkynyl” as used herein, is a subset of alkynyl and refers to a straight or branched chain hydrocarbon group containing from 2 to 4 carbon atoms.
  • Representative examples of C2-C4-alkynyl include, but are not limited, to ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-butynyl and the like.
  • Haloalkynyl as used herein, which is also expressed as “alkynyl which is partially or fully halogenated”, refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 ("C2-C 4 -haloalkynyl"), 3 to 4 (“C 3 -C 4 -haloalkynyl”) or 2 to 6 (“C2-C6-haloalkynyl”) carbon atoms and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
  • Cycloalkyl refers to a cyclic saturated hydrocarbon radical.
  • C3-C6- cycloalkyl refers to a cycloaliphatic radical having 3 to 6 carbon atoms as ring members. Examples include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • C3-Cio-cycloalkyl refers to a cycloaliphatic radical having 3 to 10 carbon atoms as ring members. Examples include, apart those mentioned above for Cs-C ⁇ -cycloalkyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
  • Cycloalkenyl refers to a cyclic non-aromatic mono- or diunsaturated hydrocarbon radical.
  • Cs-C ⁇ -cycloalkenyl refers to a cycloaliphatic mono- or diunsaturated radical having 3 to 6 carbon atoms as ring members. Examples include cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl.
  • C3-Cio-cycloalkyl refers to a cycloaliphatic mono- or diunsaturated radical having 3 to 10 carbon atoms as ring members.
  • Examples include, apart those mentioned above for Cs-C ⁇ -cycloalkenyl, cycloheptenyl, cycloheptadienyl, cyclooctenyl, cyclooctadienyl, cyclononenyl and cyclodecenyl.
  • Alkoxy refers to an alkyl radical as described above which is bound to the remainder of the molecule via an oxygen atom.
  • Ci-C 4 -alkoxy is a Ci-C 4 -alkyl group bound via an oxygen atom. Examples are methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec- butoxy, isobutoxy and tert-butoxy.
  • Ci-C6-alkoxy is a d-C ⁇ -alkyl group bound via an oxygen atom. Examples include, apart those mentioned above for Ci-C 4 -alkoxy, pentoxy, hexoxy and the positional isomers thereof.
  • Alkylthio refers to an alkyl group, as defined herein, appended to the parent molecular moiety through a sulfur atom.
  • Ci-C4-alkylthio is a Ci-C4-alkyl group bound via a sulfur atom. Examples are methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio and tert-butylthio.
  • d-C ⁇ -alkylthio is a Ci-C ⁇ -alkyl group bound via a sulfur atom. Examples include, apart those mentioned above for Ci-C4-alkylthio, pentylthio, hexylthio and the positional isomers thereof.
  • Haloalkoxy refers to an haloalkyl radical as described above which is bound to the remainder of the molecule via an oxygen atom (such as, for example, 2-fluoroethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy and the like).
  • Haloalkylthio refers to a haloalkyl group, as defined herein, appended to the parent molecular moiety through a sulfur atom.
  • Representative examples of alkylthio include, but are not limited to 2-fluoroethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, pentafluoroethylthio and the like.
  • Alkylcarbonyl refers to an alkyl group bound to the remainder of the molecule via a carbonyl group.
  • Ci-C4-alkylcarbonyl is a Ci-C4-alkyl group bound via a CO group. Examples include methylcarbonyl (acetyl), ethylcarbonyl (propionyl), propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, sec-butylcarbonyl, isobutylcarbonyl and tert- butylcarbonyl.
  • Haloalkylcarbonyl refers to a haloalkyl group bound to the remainder of the molecule via a carbonyl group.
  • Ci-C4-haloalkylcarbonyl is a Ci-C4-haloalkyl group bound via a CO group. Examples include chloromethylcarbonyl, 2-fluoroethylcarbonyl, fluoromethylcarbonyl, difluoromethylcarbonyl, trifluoromethylcarbonyl, 2,2,2-trifluoroethylcarbonyl, pentafluoroethylcarbonyl, and the like.
  • Alkoxycarbonyl refers to an alkoxy group bound to the remainder of the molecule via a carbonyl group.
  • Ci-C4-alkoxycarbonyl is a Ci-C4-alkoxy group bound via a CO group. Examples include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, isobutoxycarbonyl and tert- butoxycarbonyl.
  • Haloalkoxycarbonyl refers to a haloalkoxy radical bound to the remainder of the molecule via a carbonyl group.
  • Ci-C4-haloalkoxycarbonyl is a Ci-C4-haloalkoxy group bound via a CO group. Examples include 2-fluoroethoxycarbonyl, fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, pentafluoroethoxycarbonyl and the like.
  • Aryl or "aromatic ring moiety” refers to an aromatic hydrocarbon substituent which may be a single ring or multiple rings which are fused together, linked covalently or linked to a common group such as an ethylene or methylene moiety.
  • aryl include phenyl, naphthyl, anthracenyl, phenanthrenyl, azulenyl, indanyl, indenyl, tetrahydronaphthyl, biphenyl, diphenylmethyl and 2,2-diphenyl-1 -ethyl.
  • aryl is phenyl.
  • Aryl-Ci-C4-alkyl refers to an aromatic hydrocarbon substituent as defined above, which is bound to the remainder of the molecule via a Ci-C4-alkyl group.
  • Representative examples of aryl-Ci-C4-alkyl include benzyl and phenethyl (2-phenylethyl).
  • Aryloxy refers to an aromatic hydrocarbon substituent as defined above, which is bound to the remainder of the molecule via an oxygen atom.
  • Representative examples of aryloxy include phenoxy, naphthyloxy and tetrahydronaphthyloxy.
  • aryloxy is phenoxy.
  • Arylthio refers to an aromatic hydrocarbon substituent as defined above, which is bound to the remainder of the molecule via a sulfur atom.
  • Representative examples of aryloxy include phenylthio, naphthylthio and tetrahydronaphthylthio.
  • arylthio is phenylthio.
  • Aryloxy-Ci-C4-alkyl refers to an aromatic hydrocarbon substituent as defined above which is linked to the remainder of the molecule by O-Ci-C4-alkylene moiety such as an 0-CH 2 , 0-CH(CH 3 ), 0-CH 2 CH 2 , 0-CH(CH 3 )CH 2 or O-CH 2 -CH(CH 3 )-moiety.
  • Representative examples of aryloxy-Ci-C4-alkyl include phenoxymethyl,
  • Arylthio-Ci-C4-alkyl refers to an aromatic hydrocarbon substituent as defined above which is linked to the remainder of the molecule by S-Ci-C4-alkylene moiety such as an S-CH 2 , S-CH(CH 3 ), S-CH 2 CH 2 , S-CH(CH 3 )CH 2 or S-CH 2 -CH(CH 3 )-moiety.
  • Representative examples of aryloxy-Ci-C4-alkyl include phenylthiomethyl, 1-phenylthioethyl, 2-phenylthioethyl, 1-phenylthiopropyl, 2-phenylthiopropyl and 1 -methyl-2-phenylthioethyl.
  • Heteroaryl or “hetaryl” means a cyclic, aromatic radical in which one or more, e.g. 1 , 2, 3 or 4, ring carbon atoms have been replaced by heteroatoms such as O, S or N. If the heteroaryl group contains more than one heteroatom, the heteroatoms may be the same or different. Hetaryl may be a monocyclic or bicyclic ring.
  • Examples of monocyclic heteroaryl groups include pyrrolyl, furanyl, thienyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl and triazinyl.
  • bicyclic hetaryl groups examples include benzofuranyl, isobenzofuranyl, chromenyl, xanthenyl, indolyl, isoindolyl, indolizinyl, indazolyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, benzothiazolyl, pyrido[5,4-b]thiazolyl and benzo[b]thienyl.
  • Preferred heteroaryl groups are monocyclic 5- and 6-membered rings and contain from one to three heteroatoms independently selected from O, N, and S. Examples therefore are the monocyclic hetaryl rings listed above except for tetrazolyl. Examples are also listed below.
  • Hetaryloxy refers to hetaryl substituent as defined above, which is bound to the remainder of the molecule via an oxygen atom.
  • Examples for monocyclic hetaryloxy include pyrrolyloxy, furanyloxy, thienyloxy, pyrazolyloxy, imidazolyloxy, oxazolyloxy, isoxazolyloxy, thiazolyloxy, isothiazolyloxy, triazolyloxy, oxadiazolyloxy, thiadiazolyloxy, tetrazolyloxy, pyridyloxy, pyrimidinyloxy, pyrazinyloxy, pyridazinyloxy and triazinyloxy.
  • bicyclic hetaryloxy examples include benzofuranyloxy, isobenzofuranyloxy, chromenyloxy, xanthenyloxy, indolyloxy, isoindolyloxy, indolizinyloxy, indazolyloxy, quinolizinyloxy, isoquinolyloxy, quinolyloxy, phthalazinyloxy, naphthyridinyloxy, quinoxalinyloxy, benzothiazolyloxy, pyrido[5,4-b]thiazolyloxy and benzo[b]thienyloxy.
  • Hetaryloxyalkyl refers to an heteroaryl substituent as defined above which is linked to the remainder of the molecule by O-alkylene moiety such as an O-CH2, 0-CH(CH 3 ), 0-CH 2 CH 2 , 0-CH(CH 3 )CH 2 or O-CH 2 -CH(CH 3 )-moiety.
  • Representative examples of hetaryloxyalkyl include hetaryloxymethyl, 1-hetaryloxyethyl, 2-hetaryloxyethyl, 1-hetaryloxypropyl, 2-hetaryloxypropyl and 1-methyl- 2-hetaryloxyethyl.
  • heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO 2 , as ring members and optionally one carbonyl group as ring member
  • monocyclic radicals the monocyclic radicals being saturated, partially unsaturated or aromatic.
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • Examples of 3-, 4-, 5-, 6- or 7-membered saturated heterocyclyl include: Oxiranyl, aziridinyl, azetidinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl,
  • Examples of 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclyl include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-
  • 3-, 4-, 5-, 6- or 7-membered aromatic heterocyclyl is a 5- or 6-membered aromatic heterocyclyl (hetaryl) group containing 1 , 2, 3 or 4 heteratoms selected from O, S and N as ring members.
  • Examples are: furyl, such as 2-furyl and 3-furyl, thienyl, such as 2-thienyl and 3-thienyl, pyrrolyl, such as 2-pyrrolyl and 3-pyrrolyl, pyrazolyl, such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl, such as 2-oxazolyl, 4-oxazolyl and 5-oxazolyl, thiazolyl, such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, imidazolyl, such as 2-imidazolyl and 4-imidazolyl, triazolyl, such as 1 ,2,4-triazol-1-yl, 1 ,2,4-triazol-3-yl, 1 ,3,4-triazol-1-yl, 1 ,3,4-triazol-2-yl and the like, tetrazolyl, pyridinyl, such as 2-pyridinyl, 3-pyr
  • R 4 is hydrogen or a group which, under biological conditions, can be cleaved to give hydrogen.
  • the group OR 4 is OH or a group which under biological conditions can be cleaved to give OH.
  • examples for such groups R 4 are C1-C4- alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Cs-C ⁇ -cycloalkylcarbonyl, Ci-C4-alkoxycarbonyl, aryloxycarbonyl, Ci-C4-alkylaminocarbonyl and di-(Ci-C4-alkyl)-aminocarbonyl.
  • the carbon atom that carries the OR 4 group is a center of chirality. Therefore the compounds of the formula I may exist in the form of the S-enantiomer I-S and the R-enantiomer. In the compositions of the present invention, the compounds I may be present as pure S-enantiomer or R-enantiomer or as a mixture of the S-enantiomer or R-enantiomer in arbitrary ratios.
  • Preferred compounds of formula I are those wherein
  • R 1 and R 3 independently of each other, are hydrogen, d-C ⁇ -alkyl which may carry 1 , 2, 3 or 4 substituents R 7 , C-i-C ⁇ -haloalkyl, Cs-C ⁇ -cycloalkyl which may carry 1 , 2, 3 or 4 substituents R 8 , aryl or a 5 or 6-membered heteroaromatic ring (hetaryl) containing 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, where the cyclic moieties of the two last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4- alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro;
  • R 2 is 3-pyridinyl or 5-pyrimidinyl
  • R 4 is hydrogen or Ci-C4-alkylcarbonyl
  • R 5 and R 6 are, independently of each other, hydrogen, halogen, d-C ⁇ -alkyl, aryl or a saturated, partially unsaturated or aromatic 3- to 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members, where the cyclic moieties of the two last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy,
  • More preferred compounds of formula I are those wherein the variables R 1 , R 2 , R 3 , R 4 , R 5 and R 6 , each independently, or preferably in combination have one of the following meanings:
  • R 1 and R 3 are preferably hydrogen, d-C ⁇ -alkyl, aryl or 5 or 6-membered hetaryl containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, where the cyclic moieties of the 2 last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro.
  • R 1 and R 3 are more preferably aryl or 5 or 6-membered hetaryl containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, where the cyclic moieties of the 2 last-mentioned radicals may be unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro.
  • R 1 and R 3 independently of each other, are phenyl, pyridyl or thienyl which are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C 4 -alkyl, C 2 -C 4 -alkynyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -alkylthio, Ci-C 4 - haloalkoxy, cyano and nitro.
  • 2-fluorophenyl 2-chlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl, 4-chloro-2-fluoro- phenyl, 4-bromophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2-(trifluoromethyl)-phenyl, 3-(trifluoromethyl)-phenyl, 4-(trifluoromethyl)-phenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(trifluoromethoxy)-phenyl, 3-(trifluoromethoxy)-phenyl, 4-(trifluoromethoxy)-phenyl, 4-chloro-2-methyl
  • R 1 and R 3 are phenyl which is unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro.
  • R 1 and R 3 independently of each other, are phenyl which is unsubstituted or substituted with 1 or 2 groups selected from halogen, methyl, trifluoromethyl, methoxy or trifluoromethoxy.
  • 2-fluorophenyl 2-chlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl, 4-chloro-2-fluoro-phenyl, 4-bromophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2-(trifluoromethyl)-phenyl, 3-(trifluoromethyl)- phenyl, 4-(trifluoromethyl)-phenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(trifluoromethoxy)-phenyl, 3-(trifluoromethoxy)-phenyl,
  • R 1 and R 3 independently of each other, are phenyl which is unsubstituted or substituted with 1 or 2 halogen atoms.
  • R 1 is 2-fluorophenyl, 2-chlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2-chloro- 4-fluorophenyl or 4-chloro-2-fluoro-phenyl.
  • R 3 is 3-chlorophenyl.
  • R 2 is preferably 3-pyridinyl.
  • R 4 is preferably hydrogen.
  • R 5 and R 6 are, independently of each other, hydrogen, Ci-C ⁇ -alkyl or aryl which is unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C 4 -alkyl, C 2 -C 4 -alkynyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -alkylthio, Ci-C 4 - haloalkoxy, cyano and nitro.
  • R 5 and R 6 are, independently of each other, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl or tert-butyl. Specifically, R 5 and R 6 are hydrogen.
  • R 1 is phenyl which is unsubstituted or substituted with 1 or 2 groups selected from halogen, methyl, trifluoromethyl, methoxy or trifluoromethoxy and is preferably
  • R 2 is 3-pyridinyl
  • R 3 is 3-chlorophenyl
  • R 4 , R 5 and R 6 are hydrogen.
  • R 1 is phenyl which is substituted with 1 or 2 halogen atoms and is preferably
  • R 3 is 3-chlorophenyl
  • R 4 , R 5 and R 6 are hydrogen.
  • Examples of compounds of the present invention include, but are not limited to, the following compounds 1.1 to 1.80, listed in table A:
  • the compounds I are selected from:
  • the azoles A) are selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl, carbendazim and ethaboxam. More preferably, the azoles are selected from epoxiconazole, cyazofamid, carbendazim, prochloraz, prothioconazole and tebuconazole.
  • the strobilurins B) are selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin. More preferably, the strobilurins are selected from picoxystrobin, pyraclostrobin, trifloxystrobin, azoxylstrobin and fluoxastrobin, and even more preferably from pyraclostrobin, trifloxystrobin, azoxylstrobin and fluoxastrobin.
  • the carboxamides C) are selected from bixafen, boscalid, sedaxane, fenhexamid, metalaxyl, isopyrazam, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (picobenzamid), zoxamide, carpropamid, mandipropamid and N-(3',4',5'-tri- fluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide. More preferably, the carboxamide is boscalid.
  • the heterocyclic compounds D) are 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. More preferably, the heterocyclic compound is pyrimethanil.
  • the carbamates E) are selected from mancozeb, metiram, propineb, thiram, iprovalicarb, flubenthiavalicarb (benthiavalicarb) and propamocarb. More preferably, the carbamates are selected from iprovalicarb, propineb, flubenthiavalicarb (benthiavalicarb), mancozeb, and even more preferably from propineb and mancozeb.
  • the other active compounds F) are 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 and spiroxamine. More preferably, the other active compound F) is chlorothalonil.
  • the compounds Il are preferably selected from group A) (the above azoles), group B) (the above strobilurins) and group E) (the above carbamates). Preferred and more preferred azoles, strobilurins and carbamates are listed above. Specifically, the compounds Il are selected from cyazofamid, carbendazim, epoxiconazole, prochloraz, prothioconazole, tebuconazole, azoxystrobin, fluoxastrobin, pyraclostrobin, trifloxystrobin, mancozeb, propineb and mixtures thereof.
  • the at least one compound I and the at least one compound Il are present in synergistically effective amounts, i.e. in a weight ratio such that a synergistic effect takes place.
  • the relative amount, i.e. the weight ratio of the at least one compound I and the at least one compound Il in the composition provides for an increased fungicidal efficacy on at least one harmful fungus which exceeds the additive fungicidal efficacy of the compounds of the composition as calculated from the fungicidal efficacy of the individual compounds at a given application rate.
  • the calculation of the additive fungicidal efficacies can be performed e.g. by Colby's formula (Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, 15, 20-22, 1967). Synergism is present if the observed efficacy is greater than the calculated efficacy.
  • the at least one compound of the formula I and the at least one compound Il are usually present in the compositions of the present invention in a total weight ratio of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, even more preferably from 20:1 to 1 :20, in particular from 20:1 to 1 :10, specifically from 20:1 to 1 :5 and more specifically from 16:1 to 1 :4.
  • the composition according to the invention is preferably present in the form of a secondary or ternary composition, specifically of a secondary and tertiary mixture.
  • Secondary compositions are those which contain one compound of the formula I and one fungicidal compound of the group II.
  • Ternary compositions are those which contain one compound of the formula I and two different fungicidal compounds of the group II, hereinafter also referred to as compounds Na and lib, or two compounds of formula I, hereinafter also referred to as compounds Ia and Ib, and one fungicidal compound of the group II, the first variant being however preferred.
  • the at least one compound of the formula I and the one compound Il are usually present in a weight ratio of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, even more preferably from 20:1 to 1 :20, in particular from 20:1 to 1 :10, specifically from 20:1 to 1 :5 and more specifically from 16:1 to 1 :4.
  • the at least one compound of the formula I and the two compounds Na and Nb are usually present in a weight ratio of compound I to compounds Na + Nb of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, even more preferably from 20:1 to 1 :20, in particular from 20:1 to 1 :10, specifically from 20:1 to 1 :5 and more specifically from 16:1 to 1 :4.
  • the weight ratio of the first compound Na to the second compound Nb is usually in the range from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, in particular from 20:1 to 1 :20.
  • the two compounds of the formula I (Ia + Ib) and the compound Il are usually present in a weight ratio of compounds Ia + Ib to compounds Il of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, even more preferably from 20:1 to 1 :20, in particular from 20:1 to 1 :10, specifically from 20:1 to 1 :5 and more specifically from 16:1 to 1 :4.
  • the weight ratio of the first compound Ia to the second compound Ib is usually in the range from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, in particular from 20:1 to 1 :20.
  • compositions containing a compound I and a fungicidal compound Il selected from the list comprising azoles: cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl, carbendazim and ethaboxam.
  • a compound I selected from the list comprising azoles: cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole,
  • compositions containing a compound I and a fungicidal compound Il selected from the list comprising strobilurins: picoxystrobin, pyraclostrobin, trifloxystrobin, azoxylstrobin, fluoxastrobin, and preferably selected from pyraclostrobin, trifloxystrobin, azoxylstrobin, fluoxastrobin.
  • carboxamides bixafen, boscalid, sedaxane, fenhexamid, metalaxyl, isopyrazam, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (picobenzamid), zoxamide, carpropamid, mandipropamid
  • heterocyclic compounds fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxon
  • carbamates mancozeb, metiram, propineb, thiram, iprovalicarb, flubenthiavalicarb (benthiavalicarb) and propamocarb.
  • 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 and spiroxamine
  • secondary compositions containing a compound I and a fungicidal compound Il selected from the above azoles, strobilurins and carbamates.
  • Specific secondary compositions contain a compound of formula I and a fungicidal compound Il selected from epoxiconazole, cyazofamid, carbendazim, prochloraz, prothioconazole, tebuconazole, pyraclostrobin, trifloxystrobin, azoxylstrobin, fluoxastrobin, propineb, mancozeb.
  • a further embodiment relates to the compositions B-1 to B-246 listed in Table B, where a row of Table B corresponds in each case to a fungicidal composition comprising one of the compounds of formula I (component 1 ) individualized in the present specification and the respective further active substance from groups A) to F) (component 2) compiled in the respective row.
  • compositions described comprise the active substances in synergistically effective amounts, preferably in weight ratio of compound I to compound Il of from 500:1 to 1 :100, more preferably from 100:1 to 1 :100, even more preferably from 50:1 to 1 :50, particularly preferably from 20:1 to 1 :20, in particular from 20:1 to 1 :10, specifically from 20:1 to 1 :5 and more specifically from 16:1 to 1 :4.
  • component 2 in above Table B is selected from cyazofamid, carbendazim, epoxiconazole, prochloraz, prothioconazole, tebuconazole, azoxystrobin, fluoxastrobin, pyraclostrobin, trifloxystrobin, mancozeb and propineb.
  • compositions B-1.1 to B-246.1 wherein the compound of the formula I is the compound 1.1 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.2 to B-246.2 wherein the compound of the formula I is the compound 1.2 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.3 to B-246.3 wherein the compound of the formula I is the compound 1.3 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.4 to B-246.4 wherein the compound of the formula I is the compound 1.4 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.5 to B-246.5 wherein the compound of the formula I is the compound 1.5 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.6 to B-246.6 wherein the compound of the formula I is the compound 1.6 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.7 to B-246.7 wherein the compound of the formula I is the compound 1.7 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.8 to B-246.8 wherein the compound of the formula I is the compound 1.8 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.9 to B-246.9 wherein the compound of the formula I is the compound 1.9 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.10 to B-246.10 wherein the compound of the formula I is the compound 1.10 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.11 to B-246.1 1 wherein the compound of the formula I is the compound 1.11 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.12 to B-246.12 wherein the compound of the formula I is the compound 1.12 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.14 to B-246.14 wherein the compound of the formula I is the compound 1.14 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.15 to B-246.15 wherein the compound of the formula I is the compound 1.15 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.16 to B-246.16 wherein the compound of the formula I is the compound 1.16 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.17 to B-246.17 wherein the compound of the formula I is the compound 1.17 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.18 to B-246.18 wherein the compound of the formula I is the compound 1.18 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.19 to B-246.19 wherein the compound of the formula I is the compound 1.19 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.20 to B-246.20 wherein the compound of the formula I is the compound 1.20 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.21 to B-246.21 wherein the compound of the formula I is the compound 1.21 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.25 to B-246.25 wherein the compound of the formula I is the compound 1.25 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.26 to B-246.26 wherein the compound of the formula I is the compound 1.26 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.27 to B-246.27 wherein the compound of the formula I is the compound 1.27 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.29 to B-246.29 wherein the compound of the formula I is the compound 1.29 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.30 to B-246.30 wherein the compound of the formula I is the compound 1.30 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.31 to B-246.31 wherein the compound of the formula I is the compound 1.31 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.32 to B-246.32 wherein the compound of the formula I is the compound 1.32 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.34 to B-246.34 wherein the compound of the formula I is the compound 1.34 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.35 to B-246.35 wherein the compound of the formula I is the compound 1.35 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.36 to B-246.36 wherein the compound of the formula I is the compound 1.36 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.37 to B-246.37 wherein the compound of the formula I is the compound 1.37 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.39 to B-246.39 wherein the compound of the formula I is the compound 1.39 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.40 to B-246.40 wherein the compound of the formula I is the compound 1.40 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.41 to B-246.41 wherein the compound of the formula I is the compound 1.41 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.42 to B-246.42 wherein the compound of the formula I is the compound 1.42 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.44 to B-246.44 wherein the compound of the formula I is the compound 1.44 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.45 to B-246.45 wherein the compound of the formula I is the compound 1.45 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.46 to B-246.46 wherein the compound of the formula I is the compound 1.46 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.47 to B-246.47 wherein the compound of the formula I is the compound 1.47 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.49 to B-246.49 wherein the compound of the formula I is the compound 1.49 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.50 to B-246.50 wherein the compound of the formula I is the compound 1.50 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.51 to B-246.51 wherein the compound of the formula I is the compound 1.51 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.52 to B-246.52 wherein the compound of the formula I is the compound 1.52 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.53 to B-246.53 wherein the compound of the formula I is the compound 1.53 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.54 to B-246.54 wherein the compound of the formula I is the compound 1.54 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.55 to B-246.55 wherein the compound of the formula I is the compound 1.55 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.56 to B-246.56 wherein the compound of the formula I is the compound 1.56 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.57 to B-246.57 wherein the compound of the formula I is the compound 1.57 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.59 to B-246.59 wherein the compound of the formula I is the compound 1.59 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.60 to B-246.60 wherein the compound of the formula I is the compound 1.60 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.61 to B-246.61 wherein the compound of the formula I is the compound 1.61 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.62 to B-246.62 wherein the compound of the formula I is the compound 1.62 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.63 to B-246.63 wherein the compound of the formula I is the compound 1.63 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.64 to B-246.64 wherein the compound of the formula I is the compound 1.64 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.65 to B-246.65 wherein the compound of the formula I is the compound 1.65 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.66 to B-246.66 wherein the compound of the formula I is the compound 1.66 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.67 to B-246.67 wherein the compound of the formula I is the compound 1.67 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.69 to B-246.69 wherein the compound of the formula I is the compound 1.69 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.70 to B-246.70 wherein the compound of the formula I is the compound 1.70 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.71 to B-246.71 wherein the compound of the formula I is the compound 1.71 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.72 to B-246.72 wherein the compound of the formula I is the compound 1.72 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.73 to B-246.73 wherein the compound of the formula I is the compound 1.73 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.74 to B-246.74 wherein the compound of the formula I is the compound 1.74 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.75 to B-246.75 wherein the compound of the formula I is the compound 1.75 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.76 to B-246.76 wherein the compound of the formula I is the compound 1.76 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.77 to B-246.77 wherein the compound of the formula I is the compound 1.77 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.79 to B-246.79 wherein the compound of the formula I is the compound 1.79 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.80 to B-246.80 wherein the compound of the formula I is the compound 1.80 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
  • compositions B-1.7 to B-246.7, B-1.9 to B-246.9 B-1.10 to B-246.10, B-1.11 to B-246.1 1 , B-1.12 to B-246.12, B-1.17 to B-246.17, B-1.35 to B-246.35, B-1.61 to B-246.61 , B-1.62 to B-246.62, B-1.63 to B-246.63, B-1.64 to B-246.64, B-1.65 to B-246.65, B-1.66 to B-246.66, B-1.67 to B-246.67, B-1.68 to B-246.68, B-1.69 to B-246.69, B-1.70 to B-246.70, B-1.71 to B-246.71 , B-1.72 to B-246.72, B-1.73 to B-246.73, B-1.74 to B-246.74, B-1.75 to B-246.75, B-1.76 to B-246.76, B-1.77 to B-246.77, B-1.78 to B-246.78, B-1.79 to B-246.79 and B
  • Particular preference is given to compositions B-1.7 to B-246.7, B-1.9 to B-246.9, B-1.10 to B-246.10, B-1.11 to B-246.1 1 and B-1.12 to B-246.12.
  • the compound Il (component 2 in above Table B) is specifically selected from cyazofamid, carbendazim, epoxiconazole, prochloraz, prothioconazole, tebuconazole, azoxystrobin, fluoxastrobin, pyraclostrobin, trifloxystrobin, mancozeb and propineb.
  • compositions according to the invention or the compound I, its N-oxide or salt and the active compound II, can be converted into the customary types of agrochemical formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • agrochemical formulations for example 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 compounds used according to the invention.
  • composition types are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), 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, EC, 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, pp. 8-57 et seq., 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, further
  • methylcellulose g. methylcellulose
  • hydrophobically modified starches polyvinyl alcohols (Mowiol ® types, Clariant, Switzerland), 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.
  • anti-foaming agents examples include 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.
  • 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 active compounds and, if appropriate, further active substances, 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.
  • ammonium sulfate ammonium phosphate, ammonium nitrate, ureas
  • products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • such products may be applied to the seed diluted or undiluted.
  • a Water-soluble concentrates (SL, LS)
  • the active compounds 20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.
  • the active compound content is 20% by weight.
  • the active compounds 15 parts by weight of the active compounds 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 formulation has an active compound content of 15% by weight.
  • D Emulsions (EW, EO, ES) 25 parts by weight of the active compounds 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 (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • the formulation has an active compound content of 25% by weight.
  • the active compounds 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 compound suspension. Dilution with water gives a stable suspension of the active compound.
  • the active compound content in the formulation is 20% by weight.
  • Water-dispersible granules and water-soluble granules 50 parts by weight of the active compounds 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 (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound.
  • the formulation has an active compound content of 50% by weight.
  • Water-dispersible powders and water-soluble powders 75 parts by weight of the active compounds are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants and wetting agents as well as silica gel. Dilution with water gives a stable dispersion or solution of the active compound.
  • the active compound content of the formulation is 75% by weight.
  • 0.5 part by weight of the active compounds 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 compound content of 0.5% by weight.
  • K ULV solutions (UL) 10 parts by weight of the active compounds are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted having an active compound content of 10% by weight.
  • the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight and more preferably from 0.5 to 90% by weight, of the active compounds.
  • the active compounds are employed in a purity of from 90% to 100%, preferably 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 formulations can be applied to plant propagation materials, particularly seeds, diluted or undiluted.
  • the formulations 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 or during sowing.
  • Methods for applying or treating with agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds are known in the art, and include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • the active 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) formulation is used for seed treatment.
  • a FS formulation 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.
  • compositions of the invention can be used as such, in the form of their formulations (agrochemical compositions) or the use forms prepared therefrom, for example 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; the intention is to ensure in each case the finest possible distribution of the active compounds used 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 compound 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 %.
  • the active compounds may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations (compositions) comprising over 95% by weight of active compound, or even to apply the active compounds without additives.
  • UUV ultra-low-volume process
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, even more preferably from 0.05 to 0.75 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
  • the amount of active substances 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, pesticides such as herbicides, bactericides, other fungicides, insecticides, acaricides or nematicides, and/or growth regulators may be added to the active substances or the compositions comprising them, if appropriate not until immediately prior to use (tank mix).
  • pesticides such as herbicides, bactericides, other fungicides, insecticides, acaricides or nematicides, and/or growth regulators
  • 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 of this invention may also contain fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with the fertilizers.
  • fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners.
  • the composition of the invention also contains at least one insecticide.
  • the insecticidal compound is selected from the pyrethroids, especially alpha-cypermethrin and nicotinic receptor agonists/antagonists compounds, especially acetamiprid, clothianidine, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, and thiacloprid.
  • 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.
  • the compounds I and Il can be applied simultaneously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
  • the time interval between the treatments must be such that the desired effect can take place.
  • the time interval may be from a few seconds up to several months, for example up to 6 months. It has to be mentioned that the time interval of more than 10 days and up to several months applies especially to seed treatment where the seeds can be subjected, after having been stored for some months, e.g. for up to 6 months, to a post- treatment.
  • the time interval is from a few seconds up to several days, for example up to 6, 8 or 10 days.
  • the interval between the treatments is relatively short, i.e. the compounds I and Il are applied within a time interval of from a few seconds up to at most 3 days and in particular up to not more than one day, specifically up to not more than one hour.
  • 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. Oomycetes), 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.
  • compositions of the invention are suitable for controlling the following plant diseases:
  • Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Altemaria 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.retemata), tomatoes (e. g. A. solanior A.retemata) and wheat; Aphano- myces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A.
  • tritici anthracnose
  • Bipolaris and Drechslera spp. teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight ( ⁇ . zeicola) on corn, e. g. spot blotch ( ⁇ . sorokiniana) on cereals and e.g. B. oryzae on rice and turfs
  • Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g.
  • 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 (e.g.
  • Gray leaf spot C. zeae-maydis
  • 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
  • cereals e. g. C. herbarum (black ear) on wheat
  • Cochliobolus anamorph: Helminthosporium of Bipolaris
  • spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C.
  • sativus anamorph: B. sorokiniana
  • rice e. g. C. miyabeanus, anamorph: H. oryzae
  • Colletotrichum teleomorph: Glomerella
  • spp. anthracnose on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthi- anum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g.
  • C. sasakii sheath blight
  • Corynespora cassiicola leaf spots
  • 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.
  • vines e. g. C. liriodendri, teleomorph: Neonectria liriodendrf.
  • Phellinus punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeo- acremonium 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. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella 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.
  • vegetables e. g. E. pisi
  • cucurbits e. g. E. cichoracearum
  • cabbages rape (e. g. E. cruciferarum)
  • Eutypa lata Eutypa
  • 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
  • M. fijiensis black Sigatoka disease
  • Peronospora spp. downy mildew
  • cabbage e. g. P. brassicae
  • rape e. g. P. parasitica
  • onions e. g. P. destructor
  • tobacco e. g. P. tabacina
  • soybeans e. g. P. manshurica
  • Phakopsora pachyrhizi and P. meibomiae soybean rust
  • Phialophora spp. e. g. on vines e. g. P.
  • soybeans e. g. P. gregata: stem rot
  • Phoma lingam root and stem rot
  • P. betae root rot, leaf spot and damping-off
  • sugar beets e. g. P. viticola: can and leaf spot
  • soybeans e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum
  • Physoderma maydis brown spots
  • 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 thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: 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. feres (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. aphanidermatum); Ramularia spp., e. g. R.
  • collo-cygni (Ram u Ia ria 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. so/an/ (sheath blight) on rice or R.
  • S. miliaria head smut
  • S. sorghum und sugar cane Sphaerotheca fuliginea (powdery mildew) on cucurbits
  • Spongospora subterranea Powdery scab
  • 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
  • T. pruni plum pocket
  • 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 incamata (grey snow mold) on barley or wheat; Uro- cystis spp., e. g. U.
  • occulta stem smut
  • Uromyces spp. rust
  • 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
  • apples e. g. V. inaequalis
  • pears 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.
  • compositions of the invention are also suitable for controlling harmful fungi in the protection of materials (e. g. wood, paper, paint dispersions, fiber or fabrics) and in the protection of stored products.
  • materials e. g. wood, paper, paint dispersions, fiber or fabrics
  • harmful fungi Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp.,
  • compositions of the invention are particularly important for controlling a multitude of 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.
  • compositions of the invention 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.
  • 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.
  • treatment of plant propagation materials with compounds I and Il or with the composition of the invention 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 whose genetic material has been modified by the use of recombinant DNA techniques in such a way that under natural circumstances they 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-transitional modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • HPPD hydroxyphenylpyruvate dioxygenase
  • ALS acetolactate synthase
  • sulfonyl ureas see e. g.
  • 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, by the use of recombinant DNA techniques, are 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. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi ) or Cry ⁇ c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • insecticidal proteins especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ -endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), Cry
  • 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
  • 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 arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • 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, by the use of recombinant DNA techniques, are capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • 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).
  • PR proteins pathogenesis-related proteins
  • plant disease resistance genes e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum
  • T4-lysozym e. g. potato cultivars capable of
  • plants are also covered that, by the use of recombinant DNA techniques, are 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.
  • plants are also covered that, by the use of recombinant DNA techniques, contain 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, by the use of recombinant DNA techniques, contain 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).
  • 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 at least one compound I and the at least one compound Il are present in fungicidally effective amounts.
  • fungicidally effective amount means the amount of the compositions of the invention needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the fungicidally effective amount can vary for the various compositions used in the invention.
  • a fungicidally effective amount of the compositions will also vary according to the prevailing conditions such as desired fungicidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the compound I and the compound Il are usually applied in a weight ratio of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, even more preferably from 20:1 to 1 :20 and in particular from 10:1 to 1 :10.
  • compositions When preparing the compositions, it is preferred to employ the pure active compounds I and II, to which further active compounds against pests, such as insects, arachnids or nematodes, or herbicidal or growth-regulating active compounds or fertilizers can be added as further active components according to need.
  • pests such as insects, arachnids or nematodes, or herbicidal or growth-regulating active compounds or fertilizers
  • compositions of the invention are employed by treating the fungi or the plants, seeds, materials or soil to be protected from fungal attack with a fungicidally effective amount of the active compounds.
  • the application can be carried out both before and after the infection of the materials, plants or seeds by the fungi.
  • the application rates of the compositions according to the invention are from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, even more preferably from 0.05 to 0.75 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • compositions of the invention may also be used for improving the health of a plant.
  • the invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of the compositions of the invention.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e. g. improved plant growth and/or greener leaves ("greening effect")
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e. g. improved content or composition of certain ingredients
  • compositions of the invention can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Plant propagation materials may be treated with the composition of the invention prophylactically either at or before planting or transplanting.
  • the treatment can be made into the seedbox before planting into the field.
  • compositions of the invention have systemic action and can therefore be used for the protection of the plant shoot against foliar pests as well as for the treatment of the seed and roots against soil pests.
  • seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • compositions of the invention are also suitable for the protection of the seed and the seedlings' roots and shoots, preferably the seeds, against soil pests.
  • compositions which are especially useful for seed treatment are e.g.:
  • a Soluble concentrates (SL, LS)
  • the application rates of the composition of the invention are generally from 0.0001 to 10 kg per 100 kg of seed, dependent from the desired effect and the kind of seed.
  • Application rates are preferably from 1 to 1000 g/100 kg of seed, more preferably from 1 to 750 g/100 kg, even more preferably from 1 to 500 g/100 kg, particularly preferably from 1 to 100 g/100 kg especially from 5 to 100 g/100 kg.
  • the separate or joint application of the compounds I and Il or of the mixtures of the compounds I and Il is carried out by spraying or dusting the seeds, the seedlings, the plants or the soils before or after sowing of the plants or before or after emergence of the plants.
  • the invention also relates to the propagation products of plants, and especially the seed comprising, that is, coated with and/or containing, a mixture as defined above or a composition containing the mixture of two or more active ingredients or a mixture of two or more compositions each providing one of the active ingredients.
  • the seed comprises the compositions of the invention in an amount of from 0.1 g to 10 kg per 100 kg of seed.
  • compositions of the invention can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from fungi.
  • the content of the mixture of the active ingredients is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
  • compositions of the invention could be demonstrated by the following tests:
  • the active compounds separately or jointly, were prepared as a stock solution comprising 0.25% by weight of active compound in acetone or DMSO. 1 % by weight of the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersant action based on ethoxylated alkylphenols) was added to this solution, and the mixture was diluted with water to the desired concentration.
  • Uniperol® EL wetting agent having emulsifying and dispersant action based on ethoxylated alkylphenols
  • the efficacy (E) is calculated as follows using Abbot's formula:
  • ⁇ 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.
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • 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 Botrci cinerea in an aqueous biomalt solution was then added.
  • the plates were placed in a water vapor-saturated chamber at a temperature of 18°C.
  • 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.
  • An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing.
  • Table 1 An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated
  • the compounds of the formula I used were compounds 1.7, 1.9, 1.10, 1.11 and 1.12.
  • the fungicidal compound Il was selected from
  • - azoles epoxiconazole, prochloraz, prothioconazole, tebuconazole;
  • the stock solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the stated concentrations.
  • a spore suspension of Phytophtora infestans containing a pea juice-based aqueous nutrient medium was then added.
  • the plates were placed in a water vapor-saturated chamber at a temperature of 18°C.
  • 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.
  • An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing.
  • the test results are shown in Table 2.
  • the compounds of the formula I used were compounds 1.9 and 1.10.
  • the fungicidal compound Il was selected from
  • - strobilurins pyraclostrobin
  • 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 Pyricularia oryzae in an aqueous biomalt solution was then added.
  • the plates were placed in a water vapor-saturated chamber at a temperature of 18°C.
  • 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.
  • An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing.
  • Table 3 The results are shown in Table 3.
  • the compounds of the formula I used were compounds 1.7, 1.9, 1.10, 1.11 and 1.12.
  • the fungicidal compound Il was selected from
  • - strobilurins azoxystrobin, fluoxastrobin.
  • Use example 4 Activity against leaf blotch on wheat caused by Septoria tritici in the microtiter test (Septtr)
  • the stock solution were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the stated concentrations.
  • a spore suspension of Septoria tritici in an aqueous biomalt solution was then added.
  • the plates were placed in a water vapor-saturated chamber at temperatures of 18°C. Using an absorption photometer, the microtiter plates were measured at 405 nm on day 7 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. An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing.
  • Table 4 The test results are shown in Table 4.
  • the compound of the formula I used were compounds 1.7, 1.11 and 1.12.
  • the fungicidal compound Il was selected from - azoles: epoxiconazole, prothioconazole, tebuconazole.

Abstract

The present invention relates to compositions of fungicidally active compounds comprising at least one substituted pyrrole compound of formula I as defined below and at least one further fungicidally active compound II. The invention furthermore relates to a method for controlling harmful fungi, wherein the fungi, their habitat or the materials or plants to be protected against fungal attack, or the soil or propagation material are treated with an effective amount of at least one substituted pyrrole compound of formula I in combination with at least one compound II or with an effective amount of a composition according to the invention, to a method for protection of seed, comprising contacting the seeds with at least one compound of formula I in combination with at least one compound II, and to the use of the composition according to the invention for controlling harmful fungi.

Description

FUNGICIDAL COMPOSITIONS AND THEIR USE
Description
The present invention relates to compositions of fungicidally active compounds comprising at least one substituted pyrrole compound of formula I as defined below and at least one further fungicidally active compound II. The invention furthermore relates to a method for controlling harmful fungi, wherein the fungi, their habitat or the materials or plants to be protected against fungal attack, or the soil or propagation material are treated with an effective amount of at least one substituted pyrrole compound of formula I in combination with at least one compound Il or with an effective amount of a composition according to the invention, to a method for protection of seed, comprising contacting the seeds with at least one compound of formula I in combination with at least one compound II, and to the use of the composition according to the invention for controlling harmful fungi.
One typical problem arising in the field of fungicidal control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control.
Another problem encountered concerns the need to have available fungicidal agents which are effective against a broad spectrum of fungi.
There also exists the need for fungicidal agents that combine knock-down activity with prolonged control, that is, fast action with long lasting action.
A further problem arising with the use of fungicides is that the repeated and exclusive application of an individual fungicidal compound often leads to a rapid selection of harmful fungi which have developed natural or adapted resistance against the active compound in question. Normally, such fungi strains are also cross-resistant against other active ingredients having the same mode of action. An effective control of the pathogens with said active compounds is then not possible anymore. However, active ingredients having new mechanisms of action are difficult and expensive to develop.
Another problem underlying the present invention is the desire for compositions that improve plants, a process which is commonly and hereinafter referred to as "plant health". The term "plant health" comprises various sorts of improvements of plants that are not connected to the control of fungi. For example, advantageous properties that may be mentioned are improved crop characteristics including: emergence, crop yields, protein content, oil content, starch content, more developed root system (improved root growth), improved stress tolerance (e.g. against drought, heat, salt, UV, water, cold), reduced ethylene (reduced production and/or inhibition of reception), tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, enhanced plant vigor, increased plant stand and early and better germination; or any other advantages familiar to a person skilled in the art.
It was therefore an object of the present invention to provide fungicidal compositions which solve the problems of reducing the dosage rate and / or enhancing the spectrum of activity and / or combining knock-down activity with prolonged control and / or to resistance management and/or promoting the health of plants.
Applicants surprisingly found that these objects are in part or in whole achieved by the combination of certain fungicidal pyrrole compounds of the formula I as defined hereinafter and disclosed in WO 2008/155081 with certain other fungicidally active compounds II.
Especially, it has been found that a composition containing a compound of formula I as defined hereinafter and a compound Il as defined hereinafter show markedly enhanced action against fungi compared to the control rates that are possible with the individual compounds and/or is suitable for improving the health of plants when applied to plants, parts of plants, seeds, or at their locus of growth.
It has been found that the action of the compositions of the invention goes far beyond the fungicidal and/or plant health improving action of the active compounds present in the mixture alone.
Moreover, we have found that simultaneous, that is joint or separate, application of a compound I and a compound Il or successive application of a compound I and the compounds Il allows enhanced control of harmful fungi, compared to the control rates that are possible with the individual compounds (synergistic compositions).
Therefore the present invention relates to compositions of fungicidally active ingredients, comprising, as active components,
1 ) at least one substituted pyrrole compound of formula I
Figure imgf000004_0001
wherein:
R1 and R3, independently of each other, are hydrogen, d-Cε-alkyl which may carry 1 , 2, 3 or 4 substituents R7, d-Cε-haloalkyl, C2-C6-alkenyl which may carry 1 , 2, 3 or 4 substituents R7, C2-C6-haloalkenyl, C2-C6-alkynyl which may carry 1 , 2, 3 or 4 substituents R7, C2-C6-haloalkynyl, Cs-Cβ-cycloalkyl which may carry 1 , 2, 3 or 4 substituents R8, Cs-Cβ-cycloalkenyl which may carry 1 , 2, 3 or 4 substituents R8, tri-(Ci-C4-alkyl)-silyl, aryl, aryl-Ci-C4-alkyl, aryloxy-Ci-C4-alkyl, arylthio-Ci-C4-alkyl or a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the 5 last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4- alkylthio, Ci-C4-haloalkoxy, cyano and nitro;
with the proviso that at least one of R1 and R3 is not hydrogen;
R2 is Ci-Cβ-alkyl which may carry 1 , 2, 3 or 4 substituents R7, Ci-Cβ-haloalkyl, C2-C6-alkenyl which may carry 1 , 2, 3 or 4 substituents R7, C2-C6- haloalkenyl, C2-C6-alkynyl which may carry 1 , 2, 3 or 4 substituents R7, C2-C6-haloalkynyl, Cs-Cβ-cycloalkyl which may carry 1 , 2, 3 or 4 substituents R8, Cs-Cβ-cycloalkenyl which may carry 1 , 2, 3 or 4 substituents R8, aryl, aryl-Ci-C4-alkyl, or a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the 3 last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4- alkylthio, Ci-C4-haloalkoxy, cyano and nitro; R4 is hydrogen or a group which, under biological conditions, can be cleaved to give hydrogen;
R5 and R6 are, independently of each other, hydrogen, halogen, cyano, Ci-Cβ- alkyl which may carry 1 , 2, 3 or 4 substituents R7, d-Cε-haloalkyl, C2-C6- alkenyl which may carry 1 , 2, 3 or 4 substituents R7, C2-C6-haloalkenyl, C2-C6-alkynyl which may carry 1 , 2, 3 or 4 substituents R7, C2-C6- haloalkynyl, Cs-Cβ-cycloalkyl which may carry 1 , 2, 3 or 4 substituents R8, C3-C6-cycloalkenyl which may carry 1 , 2, 3 or 4 substituents R8, Ci-Cβ- alkoxy whose alkyl moiety may carry 1 , 2, 3 or 4 substituents R7, C-i-Cε- haloalkoxy, d-Cε-alkylthio whose alkyl moiety may carry 1 , 2, 3 or 4 substituents R7, d-Cε-haloalkylthio, Ci-C4-alkoxycarbonyl whose alkyl moiety may carry 1 , 2, 3 or 4 substituents R7, Ci-C4-haloalkoxycarbonyl, tri- (Ci-C4-alkyl)-silyl, aryl, aryl-Ci-C4-alkyl, aryloxy-Ci-C4-alkyl, arylthio-Ci-C4- alkyl or a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7- membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the 5 last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-
C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro;
R7 is hydroxyl, cyano, nitro, Cs-Cβ-cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl, Ci-C4- alkoxycarbonyl, tri-(Ci-C4-alkyl)-silyl, aryl and a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the two last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro; and
R8 is halogen, hydroxyl, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, tri-(Ci-C4-alkyl)-silyl, aryl and a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the two last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl,
Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro;
and
2) at least one fungicidal compound Il selected from:
A) azoles, selected from the group consisting of
- 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;
B) strobilurins, selected from the group consisting of 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;
C) carboxamides, selected from the group consisting of
- carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, 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-difluoromethyl-1- methyl-1 H-pyrazole-4-carboxamide, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3- dimethyl-5-fluoro-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;
D) heterocyclic compounds, selected from the group consisting of
- 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-trichloro- pyridine-2,6-di-carbonitrile, N-(1 -(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4- 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, selected from the group consisting of
- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram; - carbamates: benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamocarb hydrochloric!, valiphenal and N-(1-(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester; and F) other active compounds, selected from the group consisting of
- 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-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4- 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 and methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester;
in synergistically effective relative amounts. The invention also relates to a method for controlling harmful, preferably phytopathogenic fungi, wherein the fungi, their habitat or the materials or plants to be protected against fungal attack, or the soil or propagation material are treated with an effective amount of at least compound of formula I in combination with at least one compound II, where the compounds I and Il are as defined above or below, or with an effective amount of a composition according to the invention.
The invention furthermore relates to a method for protection of seed, comprising contacting the seeds with at least one compound of formula I in combination with at least one compound II, where the compounds I and Il are as defined above or below, in fungicidally effective amounts or with an effective amount of a composition according to the invention.
The invention also relates to the use of the composition according to the invention for controlling harmful fungi, preferably phytopathogenic fungi.
The present invention further relates to plant-protecting active ingredient compositions having synergistically enhanced action of improving the health of plants and to a method of applying such compositions of the invention to the plants.
The composition according to the invention may be a physical mixture of the at least one compound I and the at least one compound II. Accordingly, the invention also provides a mixture comprising at least one compound I and at least one compound II. However, the composition may also be any combination of at least one compound I with at least one compound II, it not being required for compounds I and Il to be present together in the same formulation.
An example of a composition according to the invention in which the at least one compound I and the at least one compound Il are not present together in the same formulation is a kit of parts. In a kit of parts, two or more components of a kit are packaged separately, i.e., not p re-formulated. As such, kits 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. One example is a two-component kit. Accordingly the present invention also relates to a two-component kit, comprising a first component which in turn comprises at least one compound I, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary, and a second component which in turn comprises at least one compound II, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary. Suitable liquid and solid carriers, surfactants and customary auxiliaries are described below.
The "combined" use of at least one compound I with and at least one compound Il or the treatment according to the invention with the at least one compound I "in combination with" at least one compound Il on the one hand can be understood as using a physical mixture of at least one compound I and at least one compound II. On the other hand, the combined use may also consist in using the at least one compound I and the at least one compound Il separately, but within a sufficiently short time of one another so that the desired effect can take place. More detailed illustrations of the combined use can be found in the specifications below.
In the context of the present invention, the term "plant" refers to an entire plant, a part of the plant or the propagation material of the plant, that is, the seed or the seedling.
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 germination 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, it takes the form of seeds.
"Locus" means a plant, seed, soil, area, material or environment in which a pest is growing or may grow.
The compounds described herein and, optionally, all their isomers may be used in the form of their salts. Within the scope of this invention, agriculturally acceptable salts are preferred.
"Agriculturally acceptable salt" means a salt the cation of which is known and accepted in the art for the formation of salts for agricultural or horticultural use. Suitable agriculturally acceptable salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Preferably the salts are water-soluble. They can be formed in a customary method, e.g. by reacting the active compound with an acid of the anion in question if the active compound has a basic functionality or by reacting an acidic active compound with a suitable base.
Because some of the compounds I have a basic center they can, for example, form acid addition salts. The same applies of course to compounds Il having a basic center. Said acid addition salts are, for example, formed with mineral acids, typically sulfuric acid, nitric acid, a phosphoric acid or a hydrogen halide, such as hydrochloric acid or hydrobromic acid, with organic carboxylic acids, typically acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, with hydroxycarboxylic acids, typically ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with organic sulfonic acids, typically methanesulfonic acid or p-toluenesulfonic acid.
Together with at least one acidic group, the compounds of formula I can also form salts with bases. Suitable salts with bases are, for example, metal salts, typically alkali metal salts; or alkaline earth metal salts, e.g. sodium salts, potassium salts or magnesium salts, or salts with ammonia or an organic amine, e.g. morpholine, piperidine, pyrrolidine, a mono-, di- or trialkylamine, typically ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or trihydroxyalkylamine, typically mono-, di- or triethanolamine. Where appropriate, the formation of corresponding internal salts is also possible.
The compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
The term Cn-Cm indicates the number of carbon atoms of an individual substituent or the respective part of a substituent.
"Halo" or "halogen", as used herein, refers to Cl, Br, I or F.
"Cyano" as used herein refers to a CN group.
"Alkyl" as used herein refers to a saturated hydrocarbon radical which may be straight- chain or branched-chain (for example, ethyl, isopropyl, t-amyl, or hexyl) and contains from 1 to 6, in particular 1 to 4 carbon atoms. This definition applies both when the term is used alone and when it is used as part of a compound term, such as "haloalkyl", "alkoxy", "alkoxyalkyl", "alkylthio" and similar terms. In some embodiments, preferred alkyl groups are those containing 1 to 4 carbon atoms. Ci-C4-alkyl is a linear or branched saturated hydrocarbon radical having 1 to 4 carbon atoms. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl. d-Cε-alkyl is a linear or branched saturated hydrocarbon radical having 1 to 6 carbon atoms. Examples are, apart those mentioned above for Ci-C4-alkyl, pentyl, hexyl and the positional isomers thereof.
"Alkylene" as used herein refers to a bivalent saturated hydrocarbon radical which is straight-chain. Alkylene is unsubstituted or may carry a substituent selected from Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and cyano. Representative examples of alkylene include, but are not limited to methylene (CHb), 1 ,1-ethandiyl, 1 ,2-ethandiyl, 1 ,1-propandiyl, 1 ,2-propandiyl, 1 ,3-propandiyl, 1 ,1-butandiyl, 1 ,2-butandiyl, 1 ,3-butandiyl, 2,3-butandiyl or 1 ,4-butandiyl.
"Haloalkyl", as used herein, refers to alkyl, as defined herein, wherein the hydrogen atoms are partly or completely replaced by halogen atoms, in particular fluorine or chlorine atoms. Representative examples of Ci-Cβ- and Ci-C4-haloalkyl include, but are not limited to, chloromethyl, 2-fluoroethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like. This definition applies both when the term is used alone and when it is used as part of a compound term, such as "haloalkyloxy", "haloalkylthio" and similar terms. In some embodiments, preferred haloalkyl groups are those containing 1 or 2 carbon atoms.
"Alkenyl" as used herein, refers to a straight or branched chain hydrocarbon containing from 2 to 6 carbons and containing at least one carbon-carbon double bond formed by the removal of two hydrogens. Representative examples of C2-C6-alkenyl include, but are not limited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, and the like. "Lower alkenyl" as used herein, is a subset of alkenyl and refers to a straight or branched chain hydrocarbon group containing from 2 to 4 carbon atoms. Representative examples of C2-C4-alkenyl include, but are not limited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, and 3-butenyl.
" Haloalkenyl" as used herein, which is also expressed as "alkenyl which is partially or fully halogenated", refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 ("C2-C4-haloalkenyl") or 2 to 6 ("C2-C6-haloalkenyl") carbon atoms and a double bond in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like. "Alkynyl" as used herein, refers to a straight or branched chain hydrocarbon group containing from 2 to 6 carbon atoms and containing at least one carbon-carbon triple bond. Representative examples of C2-C6-alkynyl include, but are not limited, to ethynyl, 1-propynyl, 2-propynyl, 3-butynyl, 1-butynyl, 1-pentynyl, 2-pentynyl, 1-hexynyl, 2-hexynyl and the like. "Lower alkynyl" as used herein, is a subset of alkynyl and refers to a straight or branched chain hydrocarbon group containing from 2 to 4 carbon atoms. Representative examples of C2-C4-alkynyl include, but are not limited, to ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-butynyl and the like.
" Haloalkynyl" as used herein, which is also expressed as "alkynyl which is partially or fully halogenated", refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 ("C2-C4-haloalkynyl"), 3 to 4 ("C3-C4-haloalkynyl") or 2 to 6 ("C2-C6-haloalkynyl") carbon atoms and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
"Cycloalkyl" as used herein refers to a cyclic saturated hydrocarbon radical. C3-C6- cycloalkyl refers to a cycloaliphatic radical having 3 to 6 carbon atoms as ring members. Examples include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
C3-Cio-cycloalkyl refers to a cycloaliphatic radical having 3 to 10 carbon atoms as ring members. Examples include, apart those mentioned above for Cs-Cβ-cycloalkyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
"Cycloalkenyl" as used herein refers to a cyclic non-aromatic mono- or diunsaturated hydrocarbon radical. Cs-Cβ-cycloalkenyl refers to a cycloaliphatic mono- or diunsaturated radical having 3 to 6 carbon atoms as ring members. Examples include cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl. C3-Cio-cycloalkyl refers to a cycloaliphatic mono- or diunsaturated radical having 3 to 10 carbon atoms as ring members. Examples include, apart those mentioned above for Cs-Cβ-cycloalkenyl, cycloheptenyl, cycloheptadienyl, cyclooctenyl, cyclooctadienyl, cyclononenyl and cyclodecenyl.
"Alkoxy" refers to an alkyl radical as described above which is bound to the remainder of the molecule via an oxygen atom. Ci-C4-alkoxy is a Ci-C4-alkyl group bound via an oxygen atom. Examples are methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec- butoxy, isobutoxy and tert-butoxy. Ci-C6-alkoxy is a d-Cε-alkyl group bound via an oxygen atom. Examples include, apart those mentioned above for Ci-C4-alkoxy, pentoxy, hexoxy and the positional isomers thereof. "Alkylthio" as used herein refers to an alkyl group, as defined herein, appended to the parent molecular moiety through a sulfur atom. Ci-C4-alkylthio is a Ci-C4-alkyl group bound via a sulfur atom. Examples are methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio and tert-butylthio. d-Cβ-alkylthio is a Ci-Cβ-alkyl group bound via a sulfur atom. Examples include, apart those mentioned above for Ci-C4-alkylthio, pentylthio, hexylthio and the positional isomers thereof.
"Haloalkoxy" refers to an haloalkyl radical as described above which is bound to the remainder of the molecule via an oxygen atom (such as, for example, 2-fluoroethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy and the like).
"Haloalkylthio" as used herein refers to a haloalkyl group, as defined herein, appended to the parent molecular moiety through a sulfur atom. Representative examples of alkylthio include, but are not limited to 2-fluoroethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, pentafluoroethylthio and the like.
"Alkylcarbonyl" refers to an alkyl group bound to the remainder of the molecule via a carbonyl group. Ci-C4-alkylcarbonyl is a Ci-C4-alkyl group bound via a CO group. Examples include methylcarbonyl (acetyl), ethylcarbonyl (propionyl), propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, sec-butylcarbonyl, isobutylcarbonyl and tert- butylcarbonyl.
"Haloalkylcarbonyl" refers to a haloalkyl group bound to the remainder of the molecule via a carbonyl group. Ci-C4-haloalkylcarbonyl is a Ci-C4-haloalkyl group bound via a CO group. Examples include chloromethylcarbonyl, 2-fluoroethylcarbonyl, fluoromethylcarbonyl, difluoromethylcarbonyl, trifluoromethylcarbonyl, 2,2,2-trifluoroethylcarbonyl, pentafluoroethylcarbonyl, and the like.
"Alkoxycarbonyl" refers to an alkoxy group bound to the remainder of the molecule via a carbonyl group. Ci-C4-alkoxycarbonyl is a Ci-C4-alkoxy group bound via a CO group. Examples include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, isobutoxycarbonyl and tert- butoxycarbonyl.
"Haloalkoxycarbonyl" refers to a haloalkoxy radical bound to the remainder of the molecule via a carbonyl group. Ci-C4-haloalkoxycarbonyl is a Ci-C4-haloalkoxy group bound via a CO group. Examples include 2-fluoroethoxycarbonyl, fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, pentafluoroethoxycarbonyl and the like.
"Aryl" or "aromatic ring moiety" refers to an aromatic hydrocarbon substituent which may be a single ring or multiple rings which are fused together, linked covalently or linked to a common group such as an ethylene or methylene moiety. Representative examples of aryl include phenyl, naphthyl, anthracenyl, phenanthrenyl, azulenyl, indanyl, indenyl, tetrahydronaphthyl, biphenyl, diphenylmethyl and 2,2-diphenyl-1 -ethyl. Preferably, aryl is phenyl.
"Aryl-Ci-C4-alkyl" refers to an aromatic hydrocarbon substituent as defined above, which is bound to the remainder of the molecule via a Ci-C4-alkyl group. Representative examples of aryl-Ci-C4-alkyl include benzyl and phenethyl (2-phenylethyl).
"Aryloxy" refers to an aromatic hydrocarbon substituent as defined above, which is bound to the remainder of the molecule via an oxygen atom. Representative examples of aryloxy include phenoxy, naphthyloxy and tetrahydronaphthyloxy. Preferably, aryloxy is phenoxy.
"Arylthio" refers to an aromatic hydrocarbon substituent as defined above, which is bound to the remainder of the molecule via a sulfur atom. Representative examples of aryloxy include phenylthio, naphthylthio and tetrahydronaphthylthio. Preferably, arylthio is phenylthio.
"Aryloxy-Ci-C4-alkyl" refers to an aromatic hydrocarbon substituent as defined above which is linked to the remainder of the molecule by O-Ci-C4-alkylene moiety such as an 0-CH2, 0-CH(CH3), 0-CH2CH2, 0-CH(CH3)CH2 or O-CH2-CH(CH3)-moiety. Representative examples of aryloxy-Ci-C4-alkyl include phenoxymethyl,
1-phenoxyethyl, 2-phenoxyethyl, 1-phenoxypropyl, 2-phenoxypropyl and 1-methyl- 2-phenoxyethyl.
"Arylthio-Ci-C4-alkyl" refers to an aromatic hydrocarbon substituent as defined above which is linked to the remainder of the molecule by S-Ci-C4-alkylene moiety such as an S-CH2, S-CH(CH3), S-CH2CH2, S-CH(CH3)CH2 or S-CH2-CH(CH3)-moiety. Representative examples of aryloxy-Ci-C4-alkyl include phenylthiomethyl, 1-phenylthioethyl, 2-phenylthioethyl, 1-phenylthiopropyl, 2-phenylthiopropyl and 1 -methyl-2-phenylthioethyl. "Heteroaryl" or "hetaryl" means a cyclic, aromatic radical in which one or more, e.g. 1 , 2, 3 or 4, ring carbon atoms have been replaced by heteroatoms such as O, S or N. If the heteroaryl group contains more than one heteroatom, the heteroatoms may be the same or different. Hetaryl may be a monocyclic or bicyclic ring. Examples of monocyclic heteroaryl groups include pyrrolyl, furanyl, thienyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl and triazinyl. Examples for bicyclic hetaryl groups include benzofuranyl, isobenzofuranyl, chromenyl, xanthenyl, indolyl, isoindolyl, indolizinyl, indazolyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, benzothiazolyl, pyrido[5,4-b]thiazolyl and benzo[b]thienyl. Preferred heteroaryl groups are monocyclic 5- and 6-membered rings and contain from one to three heteroatoms independently selected from O, N, and S. Examples therefore are the monocyclic hetaryl rings listed above except for tetrazolyl. Examples are also listed below.
"Hetaryloxy" refers to hetaryl substituent as defined above, which is bound to the remainder of the molecule via an oxygen atom. Examples for monocyclic hetaryloxy include pyrrolyloxy, furanyloxy, thienyloxy, pyrazolyloxy, imidazolyloxy, oxazolyloxy, isoxazolyloxy, thiazolyloxy, isothiazolyloxy, triazolyloxy, oxadiazolyloxy, thiadiazolyloxy, tetrazolyloxy, pyridyloxy, pyrimidinyloxy, pyrazinyloxy, pyridazinyloxy and triazinyloxy. Examples for bicyclic hetaryloxy include benzofuranyloxy, isobenzofuranyloxy, chromenyloxy, xanthenyloxy, indolyloxy, isoindolyloxy, indolizinyloxy, indazolyloxy, quinolizinyloxy, isoquinolyloxy, quinolyloxy, phthalazinyloxy, naphthyridinyloxy, quinoxalinyloxy, benzothiazolyloxy, pyrido[5,4-b]thiazolyloxy and benzo[b]thienyloxy.
"Hetaryloxyalkyl" refers to an heteroaryl substituent as defined above which is linked to the remainder of the molecule by O-alkylene moiety such as an O-CH2, 0-CH(CH3), 0-CH2CH2, 0-CH(CH3)CH2 or O-CH2-CH(CH3)-moiety. Representative examples of hetaryloxyalkyl include hetaryloxymethyl, 1-hetaryloxyethyl, 2-hetaryloxyethyl, 1-hetaryloxypropyl, 2-hetaryloxypropyl and 1-methyl- 2-hetaryloxyethyl.
The term "3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members and optionally one carbonyl group as ring member" as used herein refers to monocyclic radicals, the monocyclic radicals being saturated, partially unsaturated or aromatic. The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
Examples of 3-, 4-, 5-, 6- or 7-membered saturated heterocyclyl include: Oxiranyl, aziridinyl, azetidinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl,
2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4-oxadiazolidin-5-yl, 1 ,2,4-thiadiazolidin- 3-yl, 1 ,2,4-thiadiazolidin-5-yl, 1 ,2,4-triazolidin-3-yl, 1 ,3,4-oxadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-2-yl, 1 ,3,4-triazolidin-2-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 1 ,3-dioxan-5-yl, 1 ,4-dioxan-2-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1 ,3,5-hexahydrotriazin- 2-yl and 1 ,2,4-hexahydrotriazin-3-yl, 2-morpholinyl, 3-morpholinyl, 2-thiomorpholinyl, 3-thiomorpholinyl, 1-oxothiomorpholin-2-yl, 1-oxothiomorpholin-3-yl, 1 ,1- dioxothiomorpholin-2-yl, 1 ,1-dioxothiomorpholin-3-yl, hexahydroazepin-1-, -2-, -3- or -4-yl, hexahydrooxepinyl, hexahydro-1 ,3-diazepinyl, hexahydro-1 ,4-diazepinyl, hexahydro-1 ,3-oxazepinyl, hexahydro-1 ,4-oxazepinyl, hexahydro-1 ,3-dioxepinyl, hexahydro-1 ,4-dioxepinyl and the like.
Examples of 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclyl include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin- 3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1 -yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1 -yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyridazinyl, 2-di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyrazinyl, 1 ,3, 5-di- or tetrahydrotriazin-2-yl, 1 ,2, 4-di- or tetrahydrotriazin-3-yl, 2,3,4,5-tetrahydro[1 H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl,
3,4,5,6-tetrahydro[2H]azepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1 H]azepin- 1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1 H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydrooxepinyl, such as 2,3,4,5-tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydro-1 ,3-diazepinyl, tetrahydro-1 ,4-diazepinyl, tetrahydro-1 ,3-oxazepinyl, tetrahydro-1 ,4-oxazepinyl, tetrahydro-1 ,3-dioxepinyl and tetrahydro-1 ,4-dioxepinyl.
3-, 4-, 5-, 6- or 7-membered aromatic heterocyclyl is a 5- or 6-membered aromatic heterocyclyl (hetaryl) group containing 1 , 2, 3 or 4 heteratoms selected from O, S and N as ring members. Examples are: furyl, such as 2-furyl and 3-furyl, thienyl, such as 2-thienyl and 3-thienyl, pyrrolyl, such as 2-pyrrolyl and 3-pyrrolyl, pyrazolyl, such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl, such as 2-oxazolyl, 4-oxazolyl and 5-oxazolyl, thiazolyl, such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, imidazolyl, such as 2-imidazolyl and 4-imidazolyl, triazolyl, such as 1 ,2,4-triazol-1-yl, 1 ,2,4-triazol-3-yl, 1 ,3,4-triazol-1-yl, 1 ,3,4-triazol-2-yl and the like, tetrazolyl, pyridinyl, such as 2-pyridinyl, 3-pyridinyl and 4-pyridinyl, pyridazinyl, such as 3-pyridazinyl and 4-pyridazinyl, pyrimidinyl, such as 2-pyrimidinyl, 4-pyrimidinyl and 5-pyrimidinyl, 2-pyrazinyl and 1 ,3,5-triazinyl.
R4 is hydrogen or a group which, under biological conditions, can be cleaved to give hydrogen. In other words, the group OR4 is OH or a group which under biological conditions can be cleaved to give OH. Examples for such groups R4 are C1-C4- alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Cs-Cβ-cycloalkylcarbonyl, Ci-C4-alkoxycarbonyl, aryloxycarbonyl, Ci-C4-alkylaminocarbonyl and di-(Ci-C4-alkyl)-aminocarbonyl.
In the compounds of the formula I, the carbon atom that carries the OR4 group is a center of chirality. Therefore the compounds of the formula I may exist in the form of the S-enantiomer I-S and the R-enantiomer. In the compositions of the present invention, the compounds I may be present as pure S-enantiomer or R-enantiomer or as a mixture of the S-enantiomer or R-enantiomer in arbitrary ratios.
Figure imgf000019_0001
Preferred compounds of formula I are those wherein
R1 and R3, independently of each other, are hydrogen, d-Cε-alkyl which may carry 1 , 2, 3 or 4 substituents R7, C-i-Cε-haloalkyl, Cs-Cβ-cycloalkyl which may carry 1 , 2, 3 or 4 substituents R8, aryl or a 5 or 6-membered heteroaromatic ring (hetaryl) containing 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, where the cyclic moieties of the two last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4- alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro;
R2 is 3-pyridinyl or 5-pyrimidinyl; R4 is hydrogen or Ci-C4-alkylcarbonyl; and R5 and R6 are, independently of each other, hydrogen, halogen, d-Cε-alkyl, aryl or a saturated, partially unsaturated or aromatic 3- to 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members, where the cyclic moieties of the two last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy,
Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro;
or a salt thereof or an N-oxide thereof.
More preferred compounds of formula I are those wherein the variables R1, R2, R3, R4, R5 and R6, each independently, or preferably in combination have one of the following meanings:
R1 and R3, independently of each other, are preferably hydrogen, d-Cε-alkyl, aryl or 5 or 6-membered hetaryl containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, where the cyclic moieties of the 2 last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro. R1 and R3, independently of each other, are more preferably aryl or 5 or 6-membered hetaryl containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members, where the cyclic moieties of the 2 last-mentioned radicals may be unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro. Even more preferably, R1 and R3, independently of each other, are phenyl, pyridyl or thienyl which are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4- haloalkoxy, cyano and nitro. Among these, preference is given to 2-fluorophenyl, 2-chlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl, 4-chloro-2-fluoro- phenyl, 4-bromophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2-(trifluoromethyl)-phenyl, 3-(trifluoromethyl)-phenyl, 4-(trifluoromethyl)-phenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(trifluoromethoxy)-phenyl, 3-(trifluoromethoxy)-phenyl, 4-(trifluoromethoxy)-phenyl, 4-chloro-2-methylphenyl, 2-chloro-4-methoxyphenyl, 2-thienyl, 3-thienyl, 5-chloro- 2-thienyl, 3-pyridyl and 2-chloro-3-pyridyl.
Particularly preferably, R1 and R3, independently of each other, are phenyl which is unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro. Especially, R1 and R3, independently of each other, are phenyl which is unsubstituted or substituted with 1 or 2 groups selected from halogen, methyl, trifluoromethyl, methoxy or trifluoromethoxy. Among these, preference is given to 2-fluorophenyl, 2-chlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl, 4-chloro-2-fluoro-phenyl, 4-bromophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2-(trifluoromethyl)-phenyl, 3-(trifluoromethyl)- phenyl, 4-(trifluoromethyl)-phenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(trifluoromethoxy)-phenyl, 3-(trifluoromethoxy)-phenyl,
4-(trifluoromethoxy)-phenyl, 4-chloro-2-methylphenyl and 2-chloro-4-methoxyphenyl. In particular, R1 and R3, independently of each other, are phenyl which is unsubstituted or substituted with 1 or 2 halogen atoms.
Specifically, R1 is 2-fluorophenyl, 2-chlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2-chloro- 4-fluorophenyl or 4-chloro-2-fluoro-phenyl.
Specifically, R3 is 3-chlorophenyl. R2 is preferably 3-pyridinyl.
R4 is preferably hydrogen.
Preferably, R5 and R6 are, independently of each other, hydrogen, Ci-Cβ-alkyl or aryl which is unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4- haloalkoxy, cyano and nitro. More preferably, R5 and R6 are, independently of each other, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl or tert-butyl. Specifically, R5 and R6 are hydrogen.
Specific preference is given to compounds I, wherein
R1 is phenyl which is unsubstituted or substituted with 1 or 2 groups selected from halogen, methyl, trifluoromethyl, methoxy or trifluoromethoxy and is preferably
2-fluorophenyl, 2-chlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl, 4-chloro-2-fluoro-phenyl, 4-bromophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2-(trifluoromethyl)-phenyl, 3-(trifluoromethyl)-phenyl, 4-(trifluoromethyl)-phenyl, 2-methoxyphenyl,
3-methoxyphenyl, 4-methoxyphenyl, 2-(trifluoromethoxy)-phenyl, 3-(trifluoromethoxy)-phenyl, 4-(trifluoromethoxy)-phenyl, 4-chloro-2-methylphenyl or 2-chloro-4-methoxyphenyl and more preferably 2-fluorophenyl, 2-chlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl or 4-chloro-2- fluorophenyl;
R2 is 3-pyridinyl;
R3 is 3-chlorophenyl; and
R4, R5 and R6 are hydrogen.
More specific preference is given to compounds I, wherein
R1 is phenyl which is substituted with 1 or 2 halogen atoms and is preferably
2-fluorophenyl, 2-chlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl or 4-chloro-2-fluoro-phenyl, and is more preferably 2-fluorophenyl, 2-chlorophenyl,
3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl or 4-chloro-2- fluorophenyl, and is specifically 2-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl or 2-chloro-4-fluorophenyl; R2 is 3-pyτidinyl;
R3 is 3-chlorophenyl; and
R4, R5 and R6 are hydrogen.
Examples of compounds of the present invention include, but are not limited to, the following compounds 1.1 to 1.80, listed in table A:
Table A
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Ph = phenyl; Me = methyl; Et = ethyl; OMe = methoxy; c-Hexyl = cyclohexyl; c-Propyl cyclopropyl; lsoamyl = 3-methylbutyl
and salts and N-oxides thereof.
Amongst the compounds listed in table A, preference is given to the compounds 1.7, 1.9 to 1.12, 1.17, 1.35 and 1.61 to 1.80. More preference is given to the compounds 1.7, 1.9 to 1.12, 1.17, 1.35 and 1.73. Particular preference is given to the compounds 1.7 and 1.9 to 1.12.
Specifically, the compounds I are selected from:
- [3-(2-chlorophenyl)-1 -(3-chlorophenyl)-1 H-pyrrol-2-yl]-pyridin-3-yl-methanol
- [3-(2-fluorophenyl)-1 -(3-chlorophenyl)-1 H-pyrrol-2-yl]-pyridin-3-yl-methanol
- [3-(3-chlorophenyl)-1 -(3-chlorophenyl)-1 H-pyrrol-2-yl]-pyridin-3-yl-methanol
- [3-(4-chlorophenyl)-1 -(3-chlorophenyl)-1 H-pyrrol-2-yl]-pyridin-3-yl-methanol
- [3-(2-chloro-4-fluorophenyl)-1 -(3-chlorophenyl)-1 H-pyrrol-2-yl]-pyridin-3-yl-methanol.
The active compounds Il mentioned above, their preparation and their action against harmful fungi are generally known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. 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 03/1 1853; 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).
Preferably, the azoles A) are selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl, carbendazim and ethaboxam. More preferably, the azoles are selected from epoxiconazole, cyazofamid, carbendazim, prochloraz, prothioconazole and tebuconazole.
Preferably, the strobilurins B) are selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin. More preferably, the strobilurins are selected from picoxystrobin, pyraclostrobin, trifloxystrobin, azoxylstrobin and fluoxastrobin, and even more preferably from pyraclostrobin, trifloxystrobin, azoxylstrobin and fluoxastrobin.
Preferably, the carboxamides C) are selected from bixafen, boscalid, sedaxane, fenhexamid, metalaxyl, isopyrazam, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (picobenzamid), zoxamide, carpropamid, mandipropamid and N-(3',4',5'-tri- fluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide. More preferably, the carboxamide is boscalid.
Preferably, the heterocyclic compounds D) are 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. More preferably, the heterocyclic compound is pyrimethanil.
Preferably, the carbamates E) are selected from mancozeb, metiram, propineb, thiram, iprovalicarb, flubenthiavalicarb (benthiavalicarb) and propamocarb. More preferably, the carbamates are selected from iprovalicarb, propineb, flubenthiavalicarb (benthiavalicarb), mancozeb, and even more preferably from propineb and mancozeb.
Preferably, the other active compounds F) are 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 and spiroxamine. More preferably, the other active compound F) is chlorothalonil.
The compounds Il are preferably selected from group A) (the above azoles), group B) (the above strobilurins) and group E) (the above carbamates). Preferred and more preferred azoles, strobilurins and carbamates are listed above. Specifically, the compounds Il are selected from cyazofamid, carbendazim, epoxiconazole, prochloraz, prothioconazole, tebuconazole, azoxystrobin, fluoxastrobin, pyraclostrobin, trifloxystrobin, mancozeb, propineb and mixtures thereof.
In the compositions of the present invention, the at least one compound I and the at least one compound Il are present in synergistically effective amounts, i.e. in a weight ratio such that a synergistic effect takes place. This means that the relative amount, i.e. the weight ratio of the at least one compound I and the at least one compound Il in the composition provides for an increased fungicidal efficacy on at least one harmful fungus which exceeds the additive fungicidal efficacy of the compounds of the composition as calculated from the fungicidal efficacy of the individual compounds at a given application rate. The calculation of the additive fungicidal efficacies can be performed e.g. by Colby's formula (Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, 15, 20-22, 1967). Synergism is present if the observed efficacy is greater than the calculated efficacy.
To ensure synergism, the at least one compound of the formula I and the at least one compound Il are usually present in the compositions of the present invention in a total weight ratio of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, even more preferably from 20:1 to 1 :20, in particular from 20:1 to 1 :10, specifically from 20:1 to 1 :5 and more specifically from 16:1 to 1 :4.
According to the present invention, the composition according to the invention is preferably present in the form of a secondary or ternary composition, specifically of a secondary and tertiary mixture. Secondary compositions are those which contain one compound of the formula I and one fungicidal compound of the group II. Ternary compositions are those which contain one compound of the formula I and two different fungicidal compounds of the group II, hereinafter also referred to as compounds Na and lib, or two compounds of formula I, hereinafter also referred to as compounds Ia and Ib, and one fungicidal compound of the group II, the first variant being however preferred.
In the binary compositions of the present invention the at least one compound of the formula I and the one compound Il are usually present in a weight ratio of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, even more preferably from 20:1 to 1 :20, in particular from 20:1 to 1 :10, specifically from 20:1 to 1 :5 and more specifically from 16:1 to 1 :4.
In the ternary compositions of the present invention the at least one compound of the formula I and the two compounds Na and Nb are usually present in a weight ratio of compound I to compounds Na + Nb of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, even more preferably from 20:1 to 1 :20, in particular from 20:1 to 1 :10, specifically from 20:1 to 1 :5 and more specifically from 16:1 to 1 :4. The weight ratio of the first compound Na to the second compound Nb is usually in the range from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, in particular from 20:1 to 1 :20.
In the alternative ternary compositions of the present invention the two compounds of the formula I (Ia + Ib) and the compound Il are usually present in a weight ratio of compounds Ia + Ib to compounds Il of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, even more preferably from 20:1 to 1 :20, in particular from 20:1 to 1 :10, specifically from 20:1 to 1 :5 and more specifically from 16:1 to 1 :4. The weight ratio of the first compound Ia to the second compound Ib is usually in the range from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, in particular from 20:1 to 1 :20.
Especially preferred are secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising azoles: 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 given to those secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising azoles: epoxiconazole, cyazofamid, carbendazim, prochloraz, prothioconazole, tebuconazole. Especially preferred are secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising strobilurins: azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin. Particular preference is given to those secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising strobilurins: picoxystrobin, pyraclostrobin, trifloxystrobin, azoxylstrobin, fluoxastrobin, and preferably selected from pyraclostrobin, trifloxystrobin, azoxylstrobin, fluoxastrobin.
Especially preferred are secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising carboxamides: bixafen, boscalid, sedaxane, fenhexamid, metalaxyl, isopyrazam, 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 given to those secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising carboxamides: boscalid.
Especially preferred are secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising heterocyclic compounds: 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. Particular preference is given to those secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising heterocyclic compounds: pyrimethanil.
Especially preferred are secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising carbamates: mancozeb, metiram, propineb, thiram, iprovalicarb, flubenthiavalicarb (benthiavalicarb) and propamocarb. Particular preference is given to those secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising carbamates: iprovalicarb, propineb, flubenthiavalicarb (benthiavalicarb), mancozeb, and preferably selected from propineb, mancozeb.
Especially preferred are secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising: 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 and spiroxamine. Particular preference is given to those secondary compositions containing a compound I and a fungicidal compound Il selected from the list comprising: chlorothalonil.
Even more preferred are secondary compositions containing a compound I and a fungicidal compound Il selected from the above azoles, strobilurins and carbamates. Specific secondary compositions contain a compound of formula I and a fungicidal compound Il selected from epoxiconazole, cyazofamid, carbendazim, prochloraz, prothioconazole, tebuconazole, pyraclostrobin, trifloxystrobin, azoxylstrobin, fluoxastrobin, propineb, mancozeb.
A further embodiment relates to the compositions B-1 to B-246 listed in Table B, where a row of Table B corresponds in each case to a fungicidal composition comprising one of the compounds of formula I (component 1 ) individualized in the present specification and the respective further active substance from groups A) to F) (component 2) compiled in the respective row. The compositions described comprise the active substances in synergistically effective amounts, preferably in weight ratio of compound I to compound Il of from 500:1 to 1 :100, more preferably from 100:1 to 1 :100, even more preferably from 50:1 to 1 :50, particularly preferably from 20:1 to 1 :20, in particular from 20:1 to 1 :10, specifically from 20:1 to 1 :5 and more specifically from 16:1 to 1 :4.
Table B
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Specifically, component 2 in above Table B is selected from cyazofamid, carbendazim, epoxiconazole, prochloraz, prothioconazole, tebuconazole, azoxystrobin, fluoxastrobin, pyraclostrobin, trifloxystrobin, mancozeb and propineb.
Particular embodiments of the invention are compositions B-1.1 to B-246.1 , wherein the compound of the formula I is the compound 1.1 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.2 to B-246.2, wherein the compound of the formula I is the compound 1.2 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.3 to B-246.3, wherein the compound of the formula I is the compound 1.3 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.4 to B-246.4, wherein the compound of the formula I is the compound 1.4 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.5 to B-246.5, wherein the compound of the formula I is the compound 1.5 of table A and wherein the compound Il is the compound given in one line of table B as component 2. Particular embodiments of the invention are compositions B-1.6 to B-246.6, wherein the compound of the formula I is the compound 1.6 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.7 to B-246.7, wherein the compound of the formula I is the compound 1.7 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.8 to B-246.8, wherein the compound of the formula I is the compound 1.8 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.9 to B-246.9, wherein the compound of the formula I is the compound 1.9 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.10 to B-246.10, wherein the compound of the formula I is the compound 1.10 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.11 to B-246.1 1 , wherein the compound of the formula I is the compound 1.11 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.12 to B-246.12, wherein the compound of the formula I is the compound 1.12 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.13 to B-246.13, wherein the compound of the formula I is the compound 1.13 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.14 to B-246.14, wherein the compound of the formula I is the compound 1.14 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.15 to B-246.15, wherein the compound of the formula I is the compound 1.15 of table A and wherein the compound Il is the compound given in one line of table B as component 2. Particular embodiments of the invention are compositions B-1.16 to B-246.16, wherein the compound of the formula I is the compound 1.16 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.17 to B-246.17, wherein the compound of the formula I is the compound 1.17 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.18 to B-246.18, wherein the compound of the formula I is the compound 1.18 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.19 to B-246.19, wherein the compound of the formula I is the compound 1.19 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.20 to B-246.20, wherein the compound of the formula I is the compound 1.20 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.21 to B-246.21 , wherein the compound of the formula I is the compound 1.21 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.22 to B-246.22, wherein the compound of the formula I is the compound 1.22 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.23 to B-246.23, wherein the compound of the formula I is the compound 1.23 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.24 to B-246.24, wherein the compound of the formula I is the compound 1.24 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.25 to B-246.25, wherein the compound of the formula I is the compound 1.25 of table A and wherein the compound Il is the compound given in one line of table B as component 2. Particular embodiments of the invention are compositions B-1.26 to B-246.26, wherein the compound of the formula I is the compound 1.26 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.27 to B-246.27, wherein the compound of the formula I is the compound 1.27 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.28 to B-246.28, wherein the compound of the formula I is the compound 1.28 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.29 to B-246.29, wherein the compound of the formula I is the compound 1.29 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.30 to B-246.30, wherein the compound of the formula I is the compound 1.30 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.31 to B-246.31 , wherein the compound of the formula I is the compound 1.31 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.32 to B-246.32, wherein the compound of the formula I is the compound 1.32 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.33 to B-246.33, wherein the compound of the formula I is the compound 1.33 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.34 to B-246.34, wherein the compound of the formula I is the compound 1.34 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.35 to B-246.35, wherein the compound of the formula I is the compound 1.35 of table A and wherein the compound Il is the compound given in one line of table B as component 2. Particular embodiments of the invention are compositions B-1.36 to B-246.36, wherein the compound of the formula I is the compound 1.36 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.37 to B-246.37, wherein the compound of the formula I is the compound 1.37 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.38 to B-246.38, wherein the compound of the formula I is the compound 1.38 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.39 to B-246.39, wherein the compound of the formula I is the compound 1.39 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.40 to B-246.40, wherein the compound of the formula I is the compound 1.40 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.41 to B-246.41 , wherein the compound of the formula I is the compound 1.41 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.42 to B-246.42, wherein the compound of the formula I is the compound 1.42 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.43 to B-246.43, wherein the compound of the formula I is the compound 1.43 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.44 to B-246.44, wherein the compound of the formula I is the compound 1.44 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.45 to B-246.45, wherein the compound of the formula I is the compound 1.45 of table A and wherein the compound Il is the compound given in one line of table B as component 2. Particular embodiments of the invention are compositions B-1.46 to B-246.46, wherein the compound of the formula I is the compound 1.46 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.47 to B-246.47, wherein the compound of the formula I is the compound 1.47 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.48 to B-246.48, wherein the compound of the formula I is the compound 1.48 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.49 to B-246.49, wherein the compound of the formula I is the compound 1.49 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.50 to B-246.50, wherein the compound of the formula I is the compound 1.50 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.51 to B-246.51 , wherein the compound of the formula I is the compound 1.51 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.52 to B-246.52, wherein the compound of the formula I is the compound 1.52 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.53 to B-246.53, wherein the compound of the formula I is the compound 1.53 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.54 to B-246.54, wherein the compound of the formula I is the compound 1.54 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.55 to B-246.55, wherein the compound of the formula I is the compound 1.55 of table A and wherein the compound Il is the compound given in one line of table B as component 2. Particular embodiments of the invention are compositions B-1.56 to B-246.56, wherein the compound of the formula I is the compound 1.56 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.57 to B-246.57, wherein the compound of the formula I is the compound 1.57 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.58 to B-246.58, wherein the compound of the formula I is the compound 1.58 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.59 to B-246.59, wherein the compound of the formula I is the compound 1.59 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.60 to B-246.60, wherein the compound of the formula I is the compound 1.60 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.61 to B-246.61 , wherein the compound of the formula I is the compound 1.61 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.62 to B-246.62, wherein the compound of the formula I is the compound 1.62 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.63 to B-246.63, wherein the compound of the formula I is the compound 1.63 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.64 to B-246.64, wherein the compound of the formula I is the compound 1.64 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.65 to B-246.65, wherein the compound of the formula I is the compound 1.65 of table A and wherein the compound Il is the compound given in one line of table B as component 2. Particular embodiments of the invention are compositions B-1.66 to B-246.66, wherein the compound of the formula I is the compound 1.66 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.67 to B-246.67, wherein the compound of the formula I is the compound 1.67 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.68 to B-246.68, wherein the compound of the formula I is the compound 1.68 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.69 to B-246.69, wherein the compound of the formula I is the compound 1.69 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.70 to B-246.70, wherein the compound of the formula I is the compound 1.70 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.71 to B-246.71 , wherein the compound of the formula I is the compound 1.71 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.72 to B-246.72, wherein the compound of the formula I is the compound 1.72 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.73 to B-246.73, wherein the compound of the formula I is the compound 1.73 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.74 to B-246.74, wherein the compound of the formula I is the compound 1.74 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.75 to B-246.75, wherein the compound of the formula I is the compound 1.75 of table A and wherein the compound Il is the compound given in one line of table B as component 2. Particular embodiments of the invention are compositions B-1.76 to B-246.76, wherein the compound of the formula I is the compound 1.76 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.77 to B-246.77, wherein the compound of the formula I is the compound 1.77 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.78 to B-246.78, wherein the compound of the formula I is the compound 1.78 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.79 to B-246.79, wherein the compound of the formula I is the compound 1.79 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular embodiments of the invention are compositions B-1.80 to B-246.80, wherein the compound of the formula I is the compound 1.80 of table A and wherein the compound Il is the compound given in one line of table B as component 2.
Particular preference is given to compositions B-1.7 to B-246.7, B-1.9 to B-246.9, B-1.10 to B-246.10, B-1.11 to B-246.1 1 , B-1.12 to B-246.12, B-1.17 to B-246.17, B-1.35 to B-246.35, B-1.61 to B-246.61 , B-1.62 to B-246.62, B-1.63 to B-246.63, B-1.64 to B-246.64, B-1.65 to B-246.65, B-1.66 to B-246.66, B-1.67 to B-246.67, B-1.68 to B-246.68, B-1.69 to B-246.69, B-1.70 to B-246.70, B-1.71 to B-246.71 , B-1.72 to B-246.72, B-1.73 to B-246.73, B-1.74 to B-246.74, B-1.75 to B-246.75, B-1.76 to B-246.76, B-1.77 to B-246.77, B-1.78 to B-246.78, B-1.79 to B-246.79 and B-1.80 to B-246.80. More preference is given to compositions B-1.7 to B-246.7, B-1.9 to B-246.9, B-1.10 to B-246.10, B-1.11 to B-246.11 , B-1.12 to B-246.12, B-1.17 to B-246.17, B-1.35 to B-246.35 and B-1.73 to B-246.73. Particular preference is given to compositions B-1.7 to B-246.7, B-1.9 to B-246.9, B-1.10 to B-246.10, B-1.11 to B-246.1 1 and B-1.12 to B-246.12.
In the above particular embodiments and in the compositions of particular preference, the compound Il (component 2 in above Table B) is specifically selected from cyazofamid, carbendazim, epoxiconazole, prochloraz, prothioconazole, tebuconazole, azoxystrobin, fluoxastrobin, pyraclostrobin, trifloxystrobin, mancozeb and propineb.
Specific combinations are: - compound 1.7 in combination with prothioconazole - compound 1.7 in combination with tebuconazole
- compound 1.7 in combination with azoxystrobin
- compound 1.7 in combination with fluoxastrobin
- compound 1.7 in combination with trifloxystrobin - compound 1.7 in combination with mancozeb
- compound 1.7 in combination with propineb
- compound 1.9 in combination with carbendazim
- compound 1.9 in combination with prochloraz
- compound 1.9 in combination with pyraclostrobin - compound 1.9 in combination with mancozeb
- compound 1.10 in combination with cyazofamid
- compound 1.10 in combination with epoxiconazole
- compound 1.10 in combination with prochloraz
- compound 1.10 in combination with tebuconazole - compound 1.10 in combination with pyraclostrobin
- compound 1.10 in combination with propineb
- compound 1.11 in combination with cyazofamid
- compound 1.11 in combination with epoxiconazole
- compound 1.11 in combination with prochloraz - compound 1.11 in combination with tebuconazole
- compound 1.11 in combination with fluoxastrobin
- compound 1.12 in combination with cyazofamid
- compound 1.12 in combination with prothioconazole.
For the use according to the present invention, the compositions according to the invention, or the compound I, its N-oxide or salt and the active compound II, can be converted into the customary types of agrochemical formulations, for example 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 compounds used according to the invention.
Examples for composition types are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), 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, EC, 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, pp. 8-57 et seq., 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 ), for example by extending the active compounds with solvents and/or carriers, if desired using emulsifiers and dispersants.
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, wetters, 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, Switzerland), 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 active compounds and, if appropriate, further active substances, 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.
The following are examples of formulations:
1. Products for dilution with water
For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
A Water-soluble concentrates (SL, LS)
10 parts by weight of the active compounds are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active compound dissolves upon dilution with water. A formulation having an active compound content of 10% by weight is obtained in this manner.
B Dispersible concentrates (DC)
20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion. The active compound content is 20% by weight.
C Emulsifiable concentrates (EC)
15 parts by weight of the active compounds 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 formulation has an active compound content of 15% by weight.
D Emulsions (EW, EO, ES) 25 parts by weight of the active compounds 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 (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The formulation has an active compound content of 25% by weight.
E Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of the active compounds 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 compound suspension. Dilution with water gives a stable suspension of the active compound. The active compound content in the formulation is 20% by weight.
F Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of the active compounds 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 (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound. The formulation has an active compound content of 50% by weight.
G Water-dispersible powders and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of the active compounds are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants and wetting agents as well as silica gel. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight.
H Gel (GF)
In an agitated ball mill, 20 parts by weight of the active compounds are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of gelling agent wetters and 70 parts by weight of water or an organic solvent to give a fine suspension of the active compounds. Dilution with water gives a stable suspension of the active compounds having an active compound content of 20% by weight. 2. Products to be applied undiluted
I Dustable powders (DP, DS)
5 parts by weight of the active compounds are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having an active compound content of 5% by weight.
J Granules (GR, FG, GG, MG)
0.5 part by weight of the active compounds 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 compound content of 0.5% by weight.
K ULV solutions (UL) 10 parts by weight of the active compounds are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted having an active compound content of 10% by weight.
In general, the formulations (agrochemical compositions) comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight and more preferably from 0.5 to 90% by weight, of the active compounds. The active compounds are employed in a purity of from 90% to 100%, preferably 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 formulations can be applied to plant propagation materials, particularly seeds, diluted or undiluted. The formulations 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 or during sowing. Methods for applying or treating with agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. In a preferred embodiment, the active 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) formulation is used for seed treatment. Typically, a FS formulation 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 compositions of the invention can be used as such, in the form of their formulations (agrochemical compositions) or the use forms prepared therefrom, for example 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; the intention is to ensure in each case the finest possible distribution of the active compounds used 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 compound 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 %.
The active compounds may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations (compositions) comprising over 95% by weight of active compound, or even to apply the active compounds without additives.
When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, even more preferably from 0.05 to 0.75 kg per ha, in particular from 0.1 to 0.75 kg 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 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required. When used in the protection of materials or stored products, the amount of active substances 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, pesticides, such as herbicides, bactericides, other fungicides, insecticides, acaricides or nematicides, and/or growth regulators 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®.
Compositions of this invention may also contain fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with the fertilizers.
In one embodiment of the invention, the composition of the invention also contains at least one insecticide. Preferably, the insecticidal compound is selected from the pyrethroids, especially alpha-cypermethrin and nicotinic receptor agonists/antagonists compounds, especially acetamiprid, clothianidine, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, and thiacloprid.
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.
The compounds I and Il can be applied simultaneously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures. In the case of successive application, the time interval between the treatments must be such that the desired effect can take place. The time interval may be from a few seconds up to several months, for example up to 6 months. It has to be mentioned that the time interval of more than 10 days and up to several months applies especially to seed treatment where the seeds can be subjected, after having been stored for some months, e.g. for up to 6 months, to a post- treatment. Preferably, the time interval is from a few seconds up to several days, for example up to 6, 8 or 10 days. Preferably, the interval between the treatments is relatively short, i.e. the compounds I and Il are applied within a time interval of from a few seconds up to at most 3 days and in particular up to not more than one day, specifically up to not more than one hour.
The 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. Oomycetes), 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.
Advantageously, the compositions of the invention are suitable for controlling the following plant diseases:
Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Altemaria 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. altemata), tomatoes (e. g. A. solanior A. altemata) and wheat; Aphano- myces 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.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (β. zeicola) on corn, e. g. spot blotch (β. sorokiniana) on cereals and e.g. B. oryzae on rice 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 (e.g. Gray leaf spot: C. zeae-maydis), 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: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthi- anum) 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 liriodendrf. 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 Phaeo- acremonium 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. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella 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. oxy- sporum ou tomatoes, F. solani on soybeans and F. verticillioides on corn; Gaeumanno- myces 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; Grain- staining 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. halstediiou 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 thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: 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. feres (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. aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ram u Ia ria 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. so/an/ (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. miliaria: 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 incamata (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 compositions of the invention are also suitable for controlling harmful fungi in the protection of materials (e. g. wood, paper, paint dispersions, fiber or fabrics) and in the protection of stored products. As to the protection of wood and construction 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., Altemaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
The compositions of the invention are particularly important for controlling a multitude of 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 compositions of the invention 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.
Preferably, treatment of plant propagation materials with compounds I and Il or with the composition of the invention 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 whose genetic material has been modified by the use of recombinant DNA techniques in such a way that under natural circumstances they 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-transitional 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, by the use of recombinant DNA techniques, are 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 arthropods, 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 them are commercially available such as YieldGard® (corn cultivars producing the Cry1 Ab 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®, Bt1 1 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb 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, by the use of recombinant DNA techniques, are 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, by the use of recombinant DNA techniques, are 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, by the use of recombinant DNA techniques, contain 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, by the use of recombinant DNA techniques, contain 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).
In the compositions according to the present invention, the at least one compound I and the at least one compound Il are present in fungicidally effective amounts. In general, "fungicidally effective amount" means the amount of the compositions of the invention needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The fungicidally effective amount can vary for the various compositions used in the invention. A fungicidally effective amount of the compositions will also vary according to the prevailing conditions such as desired fungicidal effect and duration, weather, target species, locus, mode of application, and the like.
The compound I and the compound Il are usually applied in a weight ratio of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, even more preferably from 20:1 to 1 :20 and in particular from 10:1 to 1 :10.
When preparing the compositions, it is preferred to employ the pure active compounds I and II, to which further active compounds against pests, such as insects, arachnids or nematodes, or herbicidal or growth-regulating active compounds or fertilizers can be added as further active components according to need.
The compositions of the invention are employed by treating the fungi or the plants, seeds, materials or soil to be protected from fungal attack with a fungicidally effective amount of the active compounds. The application can be carried out both before and after the infection of the materials, plants or seeds by the fungi.
In the method of combating harmful fungi depending on the type of compound and the desired effect, the application rates of the compositions according to the invention are from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, even more preferably from 0.05 to 0.75 kg per ha, in particular from 0.1 to 0.75 kg per ha.
The compositions of the invention may also be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of the compositions of the invention.
The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
The application of the compositions of the invention can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
Plant propagation materials may be treated with the composition of the invention prophylactically either at or before planting or transplanting.
The treatment can be made into the seedbox before planting into the field.
Some of the compositions of the invention have systemic action and can therefore be used for the protection of the plant shoot against foliar pests as well as for the treatment of the seed and roots against soil pests. The term seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
The compositions of the invention are also suitable for the protection of the seed and the seedlings' roots and shoots, preferably the seeds, against soil pests.
Compositions which are especially useful for seed treatment are e.g.:
A Soluble concentrates (SL, LS)
D Emulsions (EW, EO, ES)
E Suspensions (SC, OD, FS) F Water-dispersible granules and water-soluble granules (WG, SG)
G Water-dispersible powders and water-soluble powders (WP, SP, WS) H Gel-Formulations (GF)
I Dustable powders (DP, DS)
Preferred are FS formulations.
In the treatment of seed, the application rates of the composition of the invention are generally from 0.0001 to 10 kg per 100 kg of seed, dependent from the desired effect and the kind of seed. Application rates are preferably from 1 to 1000 g/100 kg of seed, more preferably from 1 to 750 g/100 kg, even more preferably from 1 to 500 g/100 kg, particularly preferably from 1 to 100 g/100 kg especially from 5 to 100 g/100 kg. The separate or joint application of the compounds I and Il or of the mixtures of the compounds I and Il is carried out by spraying or dusting the seeds, the seedlings, the plants or the soils before or after sowing of the plants or before or after emergence of the plants.
The invention also relates to the propagation products of plants, and especially the seed comprising, that is, coated with and/or containing, a mixture as defined above or a composition containing the mixture of two or more active ingredients or a mixture of two or more compositions each providing one of the active ingredients. The seed comprises the compositions of the invention in an amount of from 0.1 g to 10 kg per 100 kg of seed.
The compositions of the invention can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from fungi.
For use in spray compositions, the content of the mixture of the active ingredients is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
Biological Examples
Fungicidal action
The fungicidal effect of the compositions of the invention could be demonstrated by the following tests: The active compounds, separately or jointly, were prepared as a stock solution comprising 0.25% by weight of active compound in acetone or DMSO. 1 % by weight of the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersant action based on ethoxylated alkylphenols) was added to this solution, and the mixture was diluted with water to the desired concentration.
The visually determined percentages of infected leaf areas were 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 mixtures of active compounds were determined using Colby's formula (Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, 1J5, 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
Examples
Microtests The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
Use example 1 - Activity against the grey mold Botrytis cinerea in the microtiter test (Botrci)
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 Botrci cinerea in an aqueous biomalt solution 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. An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing. The test results are shown in Table 1.
The compounds of the formula I used were compounds 1.7, 1.9, 1.10, 1.11 and 1.12. The fungicidal compound Il was selected from
- azoles: epoxiconazole, prochloraz, prothioconazole, tebuconazole;
- strobilurins: trifloxystrobin;
- carbamates: mancozeb, propineb.
Table 1
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Use example 2 - Activity against the late blight pathogen Phytophthora infestans in the microtiter test (Phytin)
The stock solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Phytophtora infestans containing a pea juice-based aqueous 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. An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing. The test results are shown in Table 2.
The compounds of the formula I used were compounds 1.9 and 1.10. The fungicidal compound Il was selected from
- strobilurins: pyraclostrobin;
- carbamates: propineb.
Table 2
Figure imgf000067_0002
Figure imgf000068_0001
Use example 3 - Activity against rice blast Pyricularia oryzae in the microtiterplate test (Pyrior)
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 Pyricularia oryzae in an aqueous biomalt solution 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. An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing. The results are shown in Table 3.
The compounds of the formula I used were compounds 1.7, 1.9, 1.10, 1.11 and 1.12. The fungicidal compound Il was selected from
- azoles: carbendazim, cyazofamid, tebuconazole;
- strobilurins: azoxystrobin, fluoxastrobin.
Table 3
Figure imgf000068_0002
Figure imgf000069_0001
Use example 4 - Activity against leaf blotch on wheat caused by Septoria tritici in the microtiter test (Septtr) The stock solution were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria tritici in an aqueous biomalt solution was then added. The plates were placed in a water vapor-saturated chamber at temperatures of 18°C. Using an absorption photometer, the microtiter plates were measured at 405 nm on day 7 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. An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing. The test results are shown in Table 4.
The compound of the formula I used were compounds 1.7, 1.11 and 1.12. The fungicidal compound Il was selected from - azoles: epoxiconazole, prothioconazole, tebuconazole.
Table 4
Figure imgf000070_0001
The test results show that by virtue of strong synergism, the activity of the mixtures according to the invention is considerably higher than had been predicted using Colby's formula.

Claims

Claims:
1. Fungicidal composition comprising, as active components,
1 ) a fungicidal compound of formula I
Figure imgf000072_0001
wherein:
R1 and R3, independently of each other, are hydrogen, d-Cε-alkyl which may carry 1 , 2, 3 or 4 substituents R7, C-i-Cε-haloalkyl, C2-C6-alkenyl which may carry 1 , 2, 3 or 4 substituents R7, C2-C6-haloalkenyl, C2-C6-alkynyl which may carry 1 , 2, 3 or 4 substituents R7, C2-C6- haloalkynyl, Cs-Cβ-cycloalkyl which may carry 1 , 2, 3 or 4 substituents R8, C3-C6-cycloalkenyl which may carry 1 , 2, 3 or 4 substituents R8, tri-(Ci-C4-alkyl)-silyl, aryl, aryl-Ci-C4-alkyl, aryloxy-Ci-C4-alkyl, arylthio-Ci-C4-alkyl or a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the 5 last- mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, C1-C4- haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro; with the proviso that at least one of R1 and R3 is not hydrogen; R2 is Ci-Cβ-alkyl which may carry 1 , 2, 3 or 4 substituents R7, Ci-Cβ- haloalkyl, C2-C6-alkenyl which may carry 1 , 2, 3 or 4 substituents R7, C2-C6-haloalkenyl, C2-C6-alkynyl which may carry 1 , 2, 3 or 4 substituents R7, C2-C6-haloalkynyl, Cs-Cβ-cycloalkyl which may carry
1 , 2, 3 or 4 substituents R8, Cs-Cβ-cycloalkenyl which may carry 1 , 2, 3 or 4 substituents R8, aryl, aryl-Ci-C4-alkyl, or a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the 3 last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4- haloalkoxy, cyano and nitro;
R4 is hydrogen or a group which, under biological conditions, can be cleaved to give hydrogen;
R5 and R6 are, independently of each other, hydrogen, halogen, cyano,
Ci-Cβ-alkyl which may carry 1 , 2, 3 or 4 substituents R7, C-i-Cβ- haloalkyl, C2-C6-alkenyl which may carry 1 , 2, 3 or 4 substituents R7,
C2-C6-haloalkenyl, C2-C6-alkynyl which may carry 1 , 2, 3 or 4 substituents R7, C2-C6-haloalkynyl, Cs-Cβ-cycloalkyl which may carry
1 , 2, 3 or 4 substituents R8, Cs-Cβ-cycloalkenyl which may carry 1 , 2, 3 or 4 substituents R8, Ci-Cβ-alkoxy whose alkyl moiety may carry 1 , 2, 3 or 4 substituents R7, Ci-Cβ-haloalkoxy, d-Cβ-alkylthio whose alkyl moiety may carry 1 , 2, 3 or 4 substituents R7, C-i-Cβ- haloalkylthio, Ci-C4-alkoxycarbonyl whose alkyl moiety may carry 1 ,
2, 3 or 4 substituents R7, Ci-C4-haloalkoxycarbonyl, tri-(Ci-C4-alkyl)- silyl, aryl, aryl-Ci-C4-alkyl, aryloxy-Ci-C4-alkyl, arylthio-Ci-C4-alkyl or a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or
7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the 5 last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro; R7 is hydroxyl, cyano, nitro, Cs-Cβ-cycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyl,
Figure imgf000073_0001
tri-(Ci-C4-alkyl)-silyl, aryl and a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom- containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the two last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro; and R8 is halogen, hydroxyl, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4- alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C1-C4- alkylcarbonyl, Ci-C4-alkoxycarbonyl, tri-(Ci-C4-alkyl)-silyl, aryl and a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or
7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the two last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro;
or a salt thereof or an N-oxide thereof;
and
2) a fungicidal compound Il selected from:
A) azoles, selected from the group consisting of 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, cyazofamid, imazalil, pefurazoate, prochloraz, triflumizol, benomyl, carbendazim, fuberidazole, thiabendazole, ethaboxam, etridiazole, hymexazole and 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-
5-yl]-2-prop-2-ynyloxy-acetamide;
B) strobilurins, selected from the group consisting of azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, 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-pheny^-cyclopropane-carboximidoylsulfanylmethy^-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;
C) carboxamides, selected from the group consisting of benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, 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-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide, N-(2-(1 ,3-dimethyl- butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide and N-(2- (1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carbox- amide, dimethomorph, flumorph, pyrimorph, flumetover, fluopicolide, fluopyram, zoxamide, N-(3-Ethyl-3,5,5-trimethyl-cyclohexyl)-3- formylamino-2-hydroxy-benzamide, carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthiofarm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide;
D) heterocyclic compounds, selected from the group consisting of 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 -(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4-dichloro- nicotinamide, N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloro- nicotinamide, bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepanipyrim, nitrapyrin, nuarimol, pyrimethanil, triforine, fenpiclonil, fludioxonil, aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, fluoroimid, iprodione, procymidone, vinclozolin, famoxadone, fenamidone, flutianil, octhilinone, probenazole, 5-amino-2-iso- propyl-3-oxo-4-ortho-tolyl-2,3-dihydro-pyrazole-1 -carbothioic acid S-allyl ester, 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]pyτimidine and 5-ethyl-6-octyl- [1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine;
E) carbamates, selected from the group consisting of ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram, benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4-cyano- phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
and
F) other active compounds, selected from the group consisting of
- 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-3-trifluoromethyl-pyrazole-1 -yl)- acetyl]-piperidin-4-yl}-thiazole-4-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 and methoxy-acetic acid 6-tert-butyl-8-fluoro- 2,3-dimethyl-quinolin-4-yl ester;
in synergistically effective amounts.
2. The composition according to claim 1 , where the composition is a mixture.
3. The composition according to any of claims 1 or 2, where in the compound of formula I
R1 and R3, independently of each other, are hydrogen, d-Cε-alkyl, C3-C6- cycloalkyl, aryl or hetaryl, where the cyclic moieties of the two last- mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, C1-C4- alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro; R2 is 3-pyridinyl or 5-pyrimidinyl; R4 is hydrogen or Ci-C4-alkylcarbonyl; and R5 and R6 are, independently of each other, hydrogen, halogen, cyano, Ci-Cβ- alkyl, aryl or a saturated, partially unsaturated or aromatic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NO, SO and SO2 as ring members and optionally also one carbonyl group as ring member, where the cyclic moieties of the two last-mentioned radicals are unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro.
4. The composition according to claim 3, where in the compound of formula I R1 is aryl which is unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- alkylthio, Ci-C4-haloalkoxy, cyano and nitro.
5. The composition according to claim 4, where in the compound of formula I R1 is phenyl substituted by 1 or 2 halogen atoms.
6. The composition according to claim 5, where in the compound of formula I R1 is 2-fluorophenyl, 2-chlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl or 4-chloro-2-fluoro-phenyl.
7. The composition according to any of the preceding claims, where in the compound of formula I R2 is 3-pyridinyl.
8. The composition according to any of the preceding claims, where in the compound of formula I R3 is aryl which is unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro.
9. The composition according to claim 8, where in the compound of formula I R3 is 3-chlorophenyl.
10. The composition according to any of the preceding claims, where in the compound of formula I R4 is hydrogen.
1 1. The composition according to any of the preceding claims, where in the compound of formula I R5 and R6 are, independently of each other, hydrogen, Ci-Cβ-alkyl or aryl which is unsubstituted or substituted with 1 , 2 or 3 radicals selected from halogen, Ci-C4-alkyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkoxy, cyano and nitro.
12. The composition according to claim 1 1 , where in the compound of formula I R5 and R6 are, independently of each other, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl or tert-butyl.
13. The composition according to claim 12, where in the compound of formula I R5 and R6 are hydrogen.
14. The composition according to any of the preceding claims, comprising a compound of the formula I selected from the group consisting of:
- [3-(2-chlorophenyl)-1 -(3-chlorophenyl)-1 H-pyrrol-2-yl]-pyridin-3-yl-methanol
- [3-(2-fluorophenyl)-1 -(3-chlorophenyl)-1 H-pyrrol-2-yl]-pyridin-3-yl-methanol - [3-(3-chlorophenyl)-1-(3-chlorophenyl)-1 H-pyrrol-2-yl]-pyridin-3-yl-methanol
- [3-(4-chlorophenyl)-1 -(3-chlorophenyl)-1 H-pyrrol-2-yl]-pyridin-3-yl-methanol
- [3-(2-chloro-4-fluorophenyl)-1 -(3-chlorophenyl)-1 H-pyrrol-2-yl]-pyridin-3-yl- methanol.
15. The composition according to any of the preceding claims, comprising as compound Il an active compound selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl, carbendazim and ethaboxam.
16. The composition according to any of claims 1 to 14, comprising as compound Il an active compound selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin.
17. The composition according to any of claims 1 to 14, comprising as compound Il an active compound selected from bixafen, boscalid, sedaxane, fenhexamid, metalaxyl, isopyrazam, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (picobenzamid), zoxamide, carpropamid, mandipropamid and N-(3',4',5'-trifluoro- biphenyl-2-yl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide.
18. The composition according to any of claims 1 to 14, comprising as compound Il an active compound 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.
19. The composition according to any of claims 1 to 14, comprising as compound Il an active compound selected from mancozeb, metiram, propineb, thiram, iprovalicarb, flubenthiavalicarb (benthiavalicarb) and propamocarb.
20. The composition according to any of claims 1 to 14, comprising as compound Il an active compound selected from dithianon, fentin salts, fosetyl, fosetyl- aluminium, H3PO3 and salts thereof, chlorthalonil, dichlofluanid, thiophanat- methyl, copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, cymoxanil, metrafenone and spiroxamine.
21. The composition according to any of claims 1 to 14, comprising as compound Il an active compound selected from boscalid, propineb, captan, epoxiconazole, benthiavalicarb, iprovalicarb, cyazofamid, pyrimethanil and pyraclostrobin.
22. The composition according to any of claims 1 to 14, comprising as compound Il an active compound selected from carbendazim, cyazofamid, epoxiconazole, prochloraz, prothioconazole, tebuconazole, azoxystrobin, fluoxastrobin, pyraclostrobin, trifloxystrobin, mancozeb and propineb.
23. The composition according to any of claims 1 to 22, further comprising an insecticidal compound.
24. The composition according to claim 23, wherein the insecticidal compound is selected from the pyrethroids, especially alpha-cypermethrin and nicotinic receptor agonists/antagonists compounds, especially acetamiprid, clothianidine, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, and thiacloprid.
25. The composition according to any of claims 1 to 24, comprising the compound I and the compound Il in a weight ratio of from 100:1 to 1 :100.
26. The composition according to any of the preceding claims, further comprising a liquid or solid carrier.
27. A method for controlling harmful fungi, wherein the fungi, their habitat or the materials or plants to be protected against fungal attack, or the soil or propagation material are treated with an effective amount of at least compound of formula I in combination with at least one compound II, where compounds I and Il are as defined in any of claims 1 to 25.
28. The method as claimed in claim 27, wherein the compounds I and Il are applied in a total amount of from 5 g/ha to 2000 g/ha.
29. The method as claimed in claims 27 or 28 wherein the compounds I and Il are applied simultaneously, that is jointly or separately, or in succession.
30. A method for protection of seed, comprising contacting the seeds with at least one compound of formula I in combination with at least one compound II, where compounds I and Il are as defined in any of claims 1 to 25, in fungicidally effective amounts.
31. A method as claimed in claim 30, wherein the compounds I and Il are applied in a total amount of from 0.01 g to 10 kg per 100 kg of seeds.
32. The use of the composition as claimed in any of claims 1 to 25 for controlling harmful fungi.
33. Seed, comprising the composition as defined in any of claims 1 to 25 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.
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