WO2009065834A2 - Fungicidal mixtures - Google Patents

Fungicidal mixtures Download PDF

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Publication number
WO2009065834A2
WO2009065834A2 PCT/EP2008/065764 EP2008065764W WO2009065834A2 WO 2009065834 A2 WO2009065834 A2 WO 2009065834A2 EP 2008065764 W EP2008065764 W EP 2008065764W WO 2009065834 A2 WO2009065834 A2 WO 2009065834A2
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WIPO (PCT)
Prior art keywords
methyl
carboxamide
pyrazole
phenyl
difluoromethyl
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PCT/EP2008/065764
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French (fr)
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WO2009065834A3 (en
Inventor
Jochen Dietz
Silke Schäfer
Egon Haden
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Basf Se
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Publication of WO2009065834A2 publication Critical patent/WO2009065834A2/en
Publication of WO2009065834A3 publication Critical patent/WO2009065834A3/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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • the present invention relates to fungicidal mixtures comprising, as active components
  • B is phenyl, naphthyl or 5- or 6-membered hetaryl wherein said hetaryl comprises one to four heteroatoms from the group consisting of O, N and S;
  • R 1 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-alkenyl, C3-Cio-haloalkenyl, C3-Cio-alkynyl or C3-Cio-haloalkynyl,
  • C3-Cio-cycloalkyl C3-Cio-cycloalkenyl, Cs-do-cycloalkynyl, phenyl, 5- or 6-membered heterocyclyl or hetaryl wherein said heterocyclyl or hetaryl comprises one to four heteroatoms from the group consisting of O, N and S;
  • R 2 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-halo- alkenyl, C3-Cio-alkynyl, C3-Cio-haloalkynyl, C3-Cio-cycloalkyl, C3-Cio-cyclo- alkenyl, C3-Cio-cycloalkynyl, phenyl, 5- or 6-membered hetaryl or heterocyclyl wherein said hetaryl or heterocyclyl comprises one to four heteroatoms from the group consisting of O, N and S; or together with R 1 or
  • R 4 is C3-C4-alkylene or C3-C4-alkenylene
  • R 3 is hydrogen, nitro, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl,
  • R 4 is hydrogen, halogen, nitro, cyano, NR'2, Ci-C4-alkyl, Ci-C4-haloalkyl, COOR', phenyl or 5- or 6-membered hetaryl or heterocyclyl; where the aliphatic chains in R 1 and/or R 2 may be substituted by one to four identical or different groups R a :
  • R a is halogen, nitro, cyano, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl,
  • R b is halogen, cyano, hydroxyl, mercapto, nitro, NR'2, Ci-Cio-alkyl, C-i-Ce-haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl or Ci-C 6 -alkoxy;
  • A) azoles such as triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triadimefon, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1 ,2,4]triazol-1-yl)- cycloheptanol; imid
  • strobilurins such as azoxystrobin, dimoxystrobin, enestroburin, fluoxa- strobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, pyribencarb, methyl (2-chloro-5-[1-(3- methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1 -(6- methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate, methyl 2-(ortho- (2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate, 3-methoxy- 2-(2-(N-(4-methoxy-phenyl)-cyclopropane-carboximidoylsulfanylmethyl)- phenyl)
  • carboxanilides benalaxyl, benalaxyl-M, benodanil, boscalid, carboxin, mepronil, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, metalaxyl, ofurace, oxadixyl, oxycarboxin, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, N-(4'-bromobiphenyl-2-yl)-4- difluoromethyl ⁇ -methylthiazole- ⁇ -carboxamide, N-(4'-trifluoromethylbi- phenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4'-chloro- 3'-fluorobiphenyl-2-yl)-4-d
  • N-(4'-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carbox- amide N-(4'-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole- 5-carboxamide, N-(4'-chloro-3'-fluorobiphenyl-2-yl)-4-difluoromethyl- 2-methylthiazole-5-carboxamide, N-(3',4'-dichloro-4-fluorobiphenyl-2-yl)- 3-difluoromethyl-1 -methylpyrazole-4-carboxamide, N-(3',4'-dichloro-5-fluo- robiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, 3,4-di- chloro-N-(2-cyanophenyl)isothiazole-5-carboxamide, N-(2',
  • D) nitrogenous heterocyclyl compounds pyridines fluazinam, pyrifenox, 3-[5-(4-chlorophenyl)-2,3-dimethylisox- azolidin-3-yl]pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine, 2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyri- dine-2,6-di-carbonitrile, N-(1 -(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4-di- chloronicotinamide, N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloro- nicotinamide; pyrimidines: bupirimate, cyprodinil,
  • 6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine 5-ethyl-6-(3,5,5-trimethyl- hexyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 6-octyl-5-propyl-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidin-7-ylamine, 5-methoxymethyl-6-octyl-[1 ,2,4]triazolo- [1 ,5-a]pyrimidin-7-ylamine, 6-octyl-5-trifluoromethyl-[1 ,2,4]triazolo[1 ,5-a]py- rimidin-7-ylamine and 5-trifluoromethyl-6-(3,5,5-trimethylhexyl)-[1 ,2,4]tri- azolo[1 ,5-
  • dithiocarbamates dithiocarbamates: ferbam, mancozeb, maneb, metiram, metam, metha- sulphocarb, propineb, thiram, zineb, ziram; carbamates: diethofencarb, benthiavalicarb, iprovalicarb, propamocarb, propamocarb hydrochlorid, valiphenal and (4-fluorophenyl) N-(1-(1-(4- cyanophenyl)ethanesulfonyl)but-2-yl)carbamate; and F) other active compounds guanidines: dodine, dodine free base, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), guazatine, guazatine-acetate; - antibiotics: kasugamycin, kasugamycin hydrochloride-
  • the invention relates to a method for controlling harmful fungi using mixtures of at least one compound I with active compounds II, and to the use of at least one compound I with active compounds Il for preparing such mixtures, and also to compositions comprising these mixtures.
  • the 5-hydroxypyrazolines, referred to above as component 1 , of the formula I, their preparation and their action against harmful fungi are known from the literature (WO 2000/20399; WO 2006/128815; WO 2006/128817; WO 2006/128824; WO 2006/128823.
  • the active compounds II, referred to above as component 2 by their common name, their preparation and their action against harmful fungi are generally known (cf.: http://www.hclrss.demon.co.uk/index.html); they are commercially available.
  • the mixtures of the compounds I and the active compounds Il are suitable in particular for controlling harmful fungi from the class of the Peronosporomycetes (syn. Oomycetes), such as Peronospora species, Phytophthora species, Plasmopara viticola and Pseudoperonospora species, in particular fungi corresponding to those mentioned above.
  • Peronosporomycetes such as Peronospora species, Phytophthora species, Plasmopara viticola and Pseudoperonospora species, in particular fungi corresponding to those mentioned above.
  • halogen fluorine, chlorine, bromine and iodine
  • alkyl saturated straight-chain or branched hydrocarbon radicals having 1 to 4, 6, 8 or 10 carbon atoms, for example d-C ⁇ -alkyl, such as methyl, ethyl, propyl, 1 -methyl- ethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 ,1-dimethyl- propyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl- pentyl, 1 ,1-dimethylbutyl, 1
  • Suitable for the mixtures according to the invention are in particular compounds of the formula I in which B is phenyl which carries a substituent in the 3-position. Moreover, preference is given to compounds I in which B is phenyl which carries a substituent in the 4-position.
  • halogen such as fluorine, chlorine or bromine, cyano, nitro, hydroxyl, amino, methoxy, Ci-C4-alkyl, such as methyl, ethyl, isopropyl, n-butyl or tert-butyl, in particular methyl or tert-butyl.
  • a further embodiment of the compounds of the formula I relates to those compounds in which A is SO2.
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 1 is Ci-Cio-alkyl or Ci-Cio-haloalkyl. Preference is given to the compounds of the formula I in which R 1 is Ci-C4-alkyl, such as methyl, ethyl, isopropyl, n-butyl or tert-butyl.
  • R 1 is Ci-C ⁇ -haloalkyl, in particular to those groups in which all hydrogen atoms are replaced by halogen atoms, such as chlorine or fluorine, in particular fluorine.
  • R 1 is particularly preferably CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , 2,2,3, 3,4,4,4-heptafluorobutyl or 2,2,3,3,4,4,5,5,5-nonafluoropentyl.
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 1 is phenyl which may be substituted by one to five, in particular one or two, identical or different groups R a .
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 1 is 5- or 6-membered hetaryl which may be substituted by one to five, in particular one or two, identical or different groups R a .
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 1 is 5- or 6-membered heterocyclyl which may be substituted by one to five identical or different groups R a .
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 2 is hydrogen.
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 2 is Ci-C4-alkyl, in particular CH3 or C2H5.
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 1 and R 2 together form a C3- or C4-alkylene chain which may be substituted by one or more, in particular one, methyl group.
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 2 and R 4 together form a C3- or C4-alkylene chain which may be substituted by one or more, in particular one, methyl group.
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 3 is hydrogen.
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 3 is Ci-C4-alkyl, in particular CH3 or C2H5.
  • R 4 is Ci-C4-alkyl, such as methyl, ethyl, isopropyl, n-butyl or tert-butyl.
  • R 4 is Ci-C ⁇ -haloalkyl
  • R 4 is particularly preferably CF3, C2F5, C3F7 or C4F9.
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 4 is Ci-C4-alkoxycarbonyl, in particular methoxycarbonyl or ethoxycarbonyl.
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 4 is phenyl which may be substituted by one to five, preferably one to four, in particular one or two, identical or different groups R b .
  • a further embodiment of the compounds of the formula I relates to those compounds in which R 4 is 5- or 6-membered hetaryl which may be substituted by one to five, preferably one to four, in particular one or two, identical or different groups R b .
  • Preferred heteraryl groups for the formula I are thienyl, furyl and pyridyl.
  • the groups mentioned for a substituent in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.
  • Table 2 Compounds of the formula I in which A is SO2 and R 3 is hydrogen and the combination of R 1 , R 2 and R 4 for a compound corresponds in each case to one row of table I.
  • the active compounds can also be used in the form of their agriculturally acceptable salts. Suitable for this purpose are usually alkali metal or alkaline earth metal salts, such as sodium salts, potassium salts or calcium salts. Moreover, the invention relates to agrochemical compositions comprising a fungicidally effective and non-phytotoxic amount of a compound of the formula I, and to their use for controlling harmful fungi.
  • an effective and non-phytotoxic amount means an amount of the agrochemical composition or the compound which is sufficient for controlling harmful fungi on crop plants and does not cause any significant damage to the crop plants treated. Such an amount may vary over a wide range and depends on numerous factors, such as, for example, the harmful fungus to be controlled, the particular crop plant, the climatic conditions and the compounds.
  • the compounds I and the active compounds Il can be applied simultaneously, that is jointly or separately, or in succession, the order, in the case of separate application, generally not having any effect on the control results.
  • the compounds I and the active compounds II, or the mixtures according to the invention can be converted into the formulations customary for agrochemical/fungicidal compositions, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • agrochemical/fungicidal compositions for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
  • compositions or their formulations are prepared in a known manner, for example by extending the active compounds with solvents and/or carriers, if desired using further auxiliaries such as emulsifiers and dispersants.
  • auxiliaries such as emulsifiers and dispersants.
  • individual compounds may also have various functions.
  • Solvents, carriers and auxiliaries suitable for this purpose are essentially:
  • aromatic solvents for example Solvesso ® products, xylene
  • paraffins for example mineral oil fractions
  • alcohols for example methanol, butanol, pentanol, benzyl alcohol
  • ketones for example cyclohexanone, gamma-butyrolactone
  • pyrrolidones NMP, NOP
  • acetates glycols, fatty acid dimethylamides, fatty acids and fatty acid esters.
  • solvent mixtures may also be used.
  • ground natural minerals for example kaolins, clays, talc, chalk
  • ground synthetic minerals for example highly disperse silica, silicates
  • emulsifiers such as nonionogenic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.
  • compositions according to the invention can be formulated in solid form or in liquid form.
  • the compositions according to the invention may also comprise auxiliaries and/or carriers customary in crop protection compositions or in compositions for the protection of materials.
  • the auxiliaries include in particular conventional surface-active substances and other additives and carriers customary in crop protection and in the protection of materials, which compounds may be solid or liquid.
  • the surface-active substances include in particular surfactants, especially those having wetting agent properties.
  • the other auxiliaries (additives) include in particular thickeners, antifoams, preservatives, antifreeze agents, stabilizers, anticaking agents or powder-flow aids and buffers.
  • Conventional surface-active substances which are suitable in principle are anionic, nonionic and amphoteric surfactants including polymer surfactants, and the molecular weight of the surfactants will typically not exceed a value of 2000 daltons and in particular 1000 daltons (number-average).
  • the anionic surfactants include, for example, carboxylates, in particular alkali metal, alkaline earth metal, and ammonium salts of fatty acids, for example potassium stearate, which are usually also referred to as soaps; acyl glutamates; sarcosinates, for example sodium lauroyl sarcosinate; taurates; methylcelluloses; alkyl phosphates, in particular alkyl esters of mono- and diphosphoric acid; sulfates, in particular alkyl sulfates and alkyl ether sulfates; sulfonates, furthermore alkyl sulfonates and alkylaryl sulfonates, in particular alkali metal, alkaline earth metal and ammonium salts of arylsulfonic acids and of alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acids, such as, for example, lignol and phenolsul
  • the abovementioned sulfonic acids are advantageously used in the form of their neutral or, if appropriate, basic salts.
  • the nonionic surfactants include, for example, fatty alcohol alkoxylates and oxoalcohol alkoxylates, in particular ethoxylates and propoxylates having degrees of alkoxylation of usually from 2 to 100 and in particular from 3 to 50, for example alkoxylates of Cs-Cso-alkanols or alk(adi)enols, for example of isotridecyl alcohol, lauryl alcohol, oleyl alcohol or stearyl alcohol, and their Ci-C4-alkyl ethers and Ci-C4-alkyl esters, for example their acetates; alkoxylated animal and/or vegetable fats and/or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates, glycerol esters,
  • amphoteric surfactants include, for example, sulfobetaines, carboxybetaines and alkyldimethylamine oxides, for example tetradecyldimethylamine oxide.
  • Other surfactants which may be mentioned here by way of example are perfluoro surfactants, silicone surfactants, phospholipids, such as, for example, lecithin or chemically modified lecithins, amino acid surfactants, for example N-lauroylglutamate.
  • Suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are 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, for example toluene, xylene, paraffin, tetrahydro- naphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
  • Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the compounds I and, if present further active compounds with at least one solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to at least one solid carrier.
  • 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, for example, 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 silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatom
  • the formulations of the compounds according to the invention comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the compounds I.
  • the compounds are preferably employed in a purity of from 90% to 100%, preferably 95% to 100%.
  • the formulations in question give, after two-to-tenfold dilution, active compound concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.
  • active compound concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.
  • 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.
  • the active compounds are comminuted with addition of 10 parts by weight of dispersants and wetters 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 wetters and made into 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, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound.
  • the active compound content of the formulation is 75% by weight.
  • Water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF) are usually used for the treatment of plant propagation material, in particular seed. These formulations can be applied to the propagation material in undiluted or, preferably, diluted form. The application can be carried out before sowing.
  • suspension formulations For seed treatment, preference is given to using suspension formulations.
  • Such formulations usually comprise from 1 to 800 g of active compound/I, from 1 to 200 g of surfactant/I, from 0 to 200 g of antifreeze agent/I, from 0 to 400 g of binder/I, from 0 to 200 g of colorants/l and solvents, preferably water.
  • Further preferred embodiments of the mixtures according to the invention relate to combinations of one of the compounds of table 1 and one of the active compounds Il below: A) azoles
  • - triazoles azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothio- conazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1 ,2,4]triazol-1-yl)-cycloheptanol; - imidazoles:
  • - carboxanilides benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fen- furam, 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-carbox- anilide, 2-chloro-N-(1 ,1 ,3-trimethyl-indan-4-yl)-nicotinamide, N-(2',4'-difluorobiphe- nyl-2-yl)-3-difluoro
  • - carboxylic morpholides dimethomorph, flumorph; benzoic acid amides: flumetover, fluopicolde, 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-py ⁇ idin-3-yl) cyclopropanecarboxylic acid amide;
  • D) heterocyclic compounds - pyridines fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyridine-2,6-di-carbo- nitrile, 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,
  • dicarboximides fluoroimid, iprodione, procymidone, vinclozolin;
  • non-aromatic 5-membered heterocycles famoxadone, fenamidone, flutianil, octhilinone, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro- pyrazole-1-carbothioic acid S-allyl ester;
  • acibenzolar-S-methyl acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methyl- sulfate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quin- oxyfen, 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-methyl- piperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a
  • - thio- and dithiocarbamates ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram; - carbamates: benthiavalicarb, diethofencarb, benthiavalicarb, iprovalicarb, propa- mocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
  • guanidine other active substances - guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
  • - antibiotics kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, poly- oxine, validamycin A
  • - nitrophenyl derivates binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen
  • organometal compounds fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
  • organophosphorus compounds edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;
  • organochlorine compounds chlorothalonil, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quinto- zene, 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;
  • acetamides acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor; - amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
  • - aryloxyphenoxypropionates clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
  • - Bipyridyls diquat, paraquat; - (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;
  • - cyclohexanediones butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim; - dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin;
  • - diphenyl ethers acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil; - imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;
  • - phenoxy acetic acids clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
  • - pyrazines chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
  • - pyridines aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;
  • - sulfonyl ureas amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chlor
  • ureas chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
  • acetolactate synthase inhibitors bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
  • organo(thio)phosphates acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
  • - carbamates alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;
  • pyrethroids allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfen- valerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin,
  • - nicotinic receptor agonists/antagonists compounds clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chloro- thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane;
  • GABA antagonist compounds endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-
  • - mitochondrial electron transport inhibitor I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
  • oxidative phosphorylation inhibitors cyhexatin, diafenthiuron, fenbutatin oxide, propargite;
  • - moulting disruptor compounds cryomazine; mixed function oxidase inhibitors: piperonyl butoxide; - sodium channel blockers: indoxacarb, metaflumizone;
  • azoles selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, pencon
  • azoles selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, propiconazole, prothioconazole, triadimefon, t
  • azoles selected from the group consisting of epoxiconazole, fluquinconazole, flutriafol, metconazole, tebuconazole, triticonazole, prochloraz and carbendazim.
  • strobilurins selected from the group consisting of azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin.
  • mixtures of a compound of the formula I with pyraclostrobin Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the C) carboxamides selected from the group consisting of fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolide (picobenzamid), zoxamide, carpropamid and mandipropamid.
  • Particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the F) other fungicides selected from the group consisting of phosphorous acid and its salts, chlorothalonil and metrafenone.
  • the active compounds mentioned in the context of the invention may also be used in the form of their agriculturally acceptable salts. These are usually alkali metal or alkaline earth metal salts, such as sodium salts, potassium salts or calcium salts.
  • mixtures of a hydroxypyrazoline and an active compound Il are used. Under certain conditions, it may be advantageous to combine a hydroxypyrazoline with two or more active compounds II. In addition, mixtures of two or more compounds I with one or more active compounds Il may also be suitable.
  • Suitable further active components in the above sense are in particular the active compounds Il mentioned at the outset and especially the preferred active compounds Il mentioned above.
  • preferred third active components are strobilurins, in particular pyraclostrobin, carboxamides, in particular boscalid, and also organophosphorus compounds, in particular phosphorous acid and its salts.
  • the compounds I and the active compounds Il can be formulated together, or they can be formulated separately and combined only in the spray liquor (tank mix), immediately prior to application.
  • the compounds of the formula I and the compositions according to the invention are suitable as fungicides for controlling harmful fungi. They are distinguished by excellent activity against a broad spectrum of phytopathogenic fungi and fungus-like pathogens from the classes of the Plasmodiophoramycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and
  • Deuteromycetes (syn. Fungi imperfecti). Some of them are systemically active and can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. In addition, they are suitable for controlling fungi and fungus-like pathogens which, inter alia, attack the wood or the roots of crop plants, in particular of grapevines, and also of woody ornamental plants, woody fruit plants and woody forest plants.
  • fungus pathogens on various crop plants such as cereals, for example wheat, rye, barley, triticale, oats or rice; beets, for example sugar beets or fodder beets; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackcurrant or gooseberries; leguminous plants, for example beans, lentils, peas, lucerne or soybeans; oil plants, for example oilseed rape, mustard, olives, sunflowers, coconuts, cocoa, castor beans, oil palms, peanuts or soybeans; cucurbits, for example pumpkins, cucumbers or melons; fiber plants, for example cotton, flax, hemp or jute; citrus fruits, for example oranges, lemons, grapefruit or mandarins; vegetable plants, for example spinach, lettuce, asparagus, cabbage plants, carrots, onions, tomatoes, potatoes, pumpkins or bell peppers
  • beets for example sugar bee
  • the compounds of the formula I and the compositions according to the invention are preferably used for controlling a large number of fungal pathogens in agricultural crops, for example potatoes, sugar beet, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, oilseed rape, leguminous fruits, sunflowers, coffee and sugar cane; fruit, grapevines and ornamental plants and vegetable plants, for example cucumbers, tomatoes, beans and pumpkins.
  • agricultural crops for example potatoes, sugar beet, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, oilseed rape, leguminous fruits, sunflowers, coffee and sugar cane
  • fruit, grapevines and ornamental plants and vegetable plants for example cucumbers, tomatoes, beans and pumpkins.
  • crop plants also includes those which have been modified by breeding, mutagenesis or genetic engineering methods.
  • Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by crossing, mutations or by natural recombination (that is recombination of the genetic information).
  • one or more genes are integrated into the genetic material of the plant in order to improve the properties of the plant.
  • crop plants also includes those plants which have become tolerant by breeding to herbicide applications (for example applications of bromoxynil or certain herbicide classes, such as HPPD inhibitors, ALS inhibitors, EPSPS inhibitors, glutamine synthetase inhibitors or imidazolinones).
  • herbicide applications for example applications of bromoxynil or certain herbicide classes, such as HPPD inhibitors, ALS inhibitors, EPSPS inhibitors, glutamine synthetase inhibitors or imidazolinones.
  • crop plants such as soy beans, cotton, corn, beets and oilseed rape, resistant to glyphosate and glufosinate have been generated, which are available under the trade names RoundupReady ® and Liberty Link ® .
  • crop plants also includes plants which, through genetic engineering, are capable of producing one or more insecticidal proteins, for example those from the bacteria strain Bacillus. These insecticidal proteins bestow upon the plants producing them tolerance to pests from all taxonomic insect classes, in particular to beetles (Coeleropta), dipterans (Diptera) and butterflies (Lepidoptera).
  • crop plants also includes plants which, through genetic engineering, are capable of producing one or more proteins causing increased resistance to bacterial, viral or fungal pathogens, such as, for example, pathogenesis-related- proteins (PR proteins, see also EP-A 0 392 225), resistance proteins (for example potato cultivars producing two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum) or T4 lysozyme (for example potato cultivars which, by producing this protein, are resistant to bacteria such as Erwinia amylvora).
  • PR proteins pathogenesis-related- proteins
  • resistance proteins for example potato cultivars producing two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum
  • T4 lysozyme for example potato cultivars which, by producing this protein, are resistant to bacteria such as Erwinia amylvora.
  • crop plants also includes plants whose productivity has been improved through genetic engineering, for example by increasing the yield potential (for example biomass, grain yield, starch, oil or protein content), tolerance to drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens.
  • yield potential for example biomass, grain yield, starch, oil or protein content
  • tolerance to drought for example drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens.
  • crop plants also includes plants whose ingredients have been modified through genetic engineering in particular for improving human or animal diet, where, for example, oil plants produce health-promoting long-chain omega-3 fatty acids or monounsaturated omega-9 fatty acids (for example Nexera ® oilseed rape).
  • crop plants also includes plants modified by genetic engineering for improved production of raw materials, for example by increasing the amylopectin content of potatoes.
  • the compounds of the formula I and the compositions according to the invention are suitable for controlling the following plant diseases: Albugo spp. (white rust) on ornamental plants, vegetable crops (for example A.
  • Candida and sunflowers (for example A. tragopogonis),
  • Alternaria spp. black spot disease, black blotch
  • vegetables oilseed rape (for example A. brassicola or A. brassicae), sugar beet (for example A. tenuis), fruit, rice, soybeans and also on potatoes (for example A. solani or A. alternata) and tomatoes (for example A. solani or A. alternata) and Alternaria spp. (black head) on wheat,
  • Ascochyta spp. on cereals and vegetables for example A. tritici (leaf blight) on wheat and A. hordei on barley,
  • Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.) on corn (for example D. maydis), cereals (for example B. sorokiniana: brown leaf spot), rice (for example
  • Botryosphaeria spp. ('Black Dead Arm Disease') on grapevines (for example B. obtusa),
  • Botrytis cinerea (teleomorph: Botryotinia fuckeliana: gray mold, gray rot) on soft fruit and pome fruit (inter alia strawberries), vegetables (inter alia lettuce, carrots, celeriac and cabbage), oilseed rape, flowers, grapevines, forest crops and wheat (ear mold),
  • Bremia lactucae downy mildew
  • Ceratocystis syn. Ophiostoma
  • spp. blue stain fungus
  • deciduous trees and coniferous trees for example C. ulmi (Dutch elm disease) on elms
  • Cercospora spp. (Cercospora leaf spot) on corn, rice, sugar beet (for example
  • Cladosporium spp. on tomato for example C. fulvum: tomato leaf mold
  • cereals for example C. herbarum (ear rot) on wheat
  • Colletotrichum teleomorph: Glomerella
  • spp. anthracnosis
  • cotton for example C. gossypii
  • corn for example C. graminicola: stem rot and anthracnosis
  • soft fruit for example C. coccodes: wilt disease
  • beans for example C. lindemuthianum
  • soybeans for example Colletotrichum truncatum
  • Corticium spp. for example C. sasakii (sheath blight) on rice, Corynespora cassiicola (leaf spot) on soybeans and ornamental plants
  • Cycloconium spp. for example C. oleaginum on olive
  • Cylindrocarpon spp. for example fruit tree cancer or black foot disease of grapevine, teleomorph: Nectria or Neonectria spp.
  • grapevines for example C. liriodendri, teleomorph: Neonectria liriodendri, black foot disease
  • Dematophora teleomorph: Rosellinia necatrix (root/stem rot) on soybeans
  • Formitiporia punctata
  • F. mediterranea Phaeomoniella chlamydospora (old name Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa
  • Phaeomoniella chlamydospora old name Phaeoacremonium chlamydosporum
  • Phaeoacremonium aleophilum and/or Botryosphaeria obtusa
  • Erysiphe spp. (powdery mildew) on sugar beet (E. betae), vegetables (for example E. pisi), such as cucumber species (for example E. cichoracearum) and cabbage species, such as oilseed rape (for example E. cruciferarum)
  • E. betae sugar beet
  • vegetables for example E. pisi
  • cucumber species for example E. cichoracearum
  • cabbage species such as oilseed rape (for example E. cruciferarum)
  • Eutypa lata (Eutypa cancer or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees , grapevines and many ornamental trees,
  • Exserohilum (syn. Helminthosporium) spp. on corn (for example E. turcicum), Fusarium (teleomorph: Gibberella) spp. (wilt disease, root and stem rot) on various plants, such as for example F. graminearum or F. culmorum (root rot and silver-top) on cereals (for example wheat or barley), F. oxysporum on tomatoes, Fusarium solani on soybeans and F. verticillioides on corn,
  • Gaeumannomyces graminis (take-all) on cereals (for example wheat or barley) and corn,
  • Gymnosporangium spp. on Rosaceae and juniper for example G. sabinae (pear rust) on pears, Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice,
  • Hemileia spp. for example Hemileia vastatrix (coffee leaf rust) on coffee, lsariopsis clavispora (syn. Cladosporium vitis) on grapevines, Macrophomina phaseolina (syn. phaseoli) (root/stem rot) on soybeans and cotton, Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (for example wheat or barley),
  • Monilinia spp. for example M. laxa, M. fructicola and M. fructigena (blossom and twig blight) on stone fruit and other Rosaceae, Mycosphaerella spp. on cereals, bananas, soft fruit and peanuts, such as for example M. graminicola (anamorph: Septoria tritici, Septoria leaf blotch) on wheat or M. fijiensis (sigatoka disease) on bananas,
  • Peronospora spp. downy mildew on cabbage (for example P. brassicae), oilseed rape (for example P. parasitica), bulbous plants (for example P. destructor), tobacco (P. tabacina) and soybeans (for example P. manshurica),
  • Phakopsora pachyrhizi and P. meibomiae on soybeans
  • Phialophora spp. for example on grapevines (for example P. tracheiphila and P. tetraspora) and soybeans (for example P. gregata: stem disease)
  • grapevines for example P. tracheiphila and P. tetraspora
  • soybeans for example P. gregata: stem disease
  • Physoderma zeamaydis (brown spot) on corn, Phytophthora spp. (wilt disease, root, leaf, stem and fruit rot) on various plants, such as on bell peppers and cucumber species (for example P. capsici), soybeans (for example P. megasperma, syn. P. sojae), potatoes and tomatoes (for example P. infestans: late blight and brown rot) and deciduous trees (for example P. ramorum: sudden oak death) Plasmodiophora brassicae (club-root) on cabbage, oilseed rape, radish and other plants,
  • Plasmopara spp. for example P. viticola (peronospora of grapevines, downy mildew) on grapevines and P. halstedii on sunflowers, Podosphaera spp. (powdery mildew) on Rosaceae, hops, pome fruit and soft fruit, for example P. leucotricha on apple,
  • Polymyxa spp. for example on cereals, such as barley and wheat (P. graminis) and sugar beet (P. betae) and the viral diseases transmitted thereby, Pseudocercosporella herpotrichoides (eyespot/stem break, teleomorph: Tapesia yallundae) on cereals, for example wheat or barley,
  • Pseudopezicula tracheiphila angular leaf scorch, anamorph: Phialophora
  • Puccinia spp. rust disease on various plants, for example P. triticina (brown rust of wheat), P. striiformis (yellow rust), P. hordei (dwarf leaf rust of barley), P. graminis (black rust) or P. recondita (brown rust of rye) on cereals, such as for example wheat, barley or rye, and on asparagus (for example P. asparagi), Pyrenophora tritici-repentis (speckled leaf blotch) on wheat and P. teres (net blotch) on barley,
  • P. triticina brown rust of wheat
  • P. striiformis yellow rust
  • P. hordei dwarf leaf rust of barley
  • P. graminis black rust
  • P. recondita brown rust of rye
  • cereals such as for example wheat, barley or rye
  • asparagus
  • Pyricularia spp. for example P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on lawn and cereals,
  • Pythium spp. (damping-off disease) on lawn, rice, corn, wheat, cotton, oilseed rape, sunflowers, sugar beet, vegetables and other plants (for example P. ultimum or P. aphanidermatum),
  • Ramularia spp. for example R. collo-cygni (Ramularia leaf and awn spot / physiological leaf spot) on barley and R. beticola on sugar beet,
  • Rhizoctonia spp. on cotton, rice, potatoes, lawn, corn, oilseed rape, potatoes, sugar beet, vegetables and on various other plants, for example R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (sharp eyespot) on wheat or barley,
  • Rhizopus stolonifer soft rot on strawberries, carrots, cabbage and tomato
  • Rhynchosporium secalis (leaf spot) on barley, rye and triticale, Sarocladium oryzae and S. attenuatum (sheath rot) on rice,
  • Sclerotinia spp. on vegetable and field crops such as oilseed rape, sunflowers (for example Sclerotinia sclerotiorum: stem disease) and soybeans (for example Sclerotinia rolfsii: stem disease),
  • Septoria spp. on various plants, for example S. glycines (leaf spot) on soybean, S. tritici (Septoria leaf blotch) on wheat and S. (syn. Stagonospora) nodorum (leaf blotch and glume blotch) on cereals,
  • Setosphaeria spp. (leaf spot) on corn (for example S. turcicum, syn. Helminthosporium turcicum) and lawn,
  • Sphacelotheca spp. head smut
  • corn for example S. reiliana: kernel smut
  • millet millet and sugar cane
  • Stagonospora spp. on cereals for example S. nodorum (leaf blotch and glume blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat, Synchytrium endobioticum on potatoes (potato wart disease),
  • T. deformans curly-leaf disease
  • T. pruni plum-pocket disease
  • Thielaviopsis spp. black root rot
  • tobacco, pome fruit, vegetable crops, soybeans and cotton for example T. basicola (syn. Chalara elegans), Tilletia spp. (bunt or stinking smut) on cereals, such as for example T. tritici (syn.
  • Urocystis spp. for example U. occulta (flag smut) on rye
  • Uromyces spp. rust on vegetable plants, such as beans (for example U. appendiculatus, syn. U. phaseoli) and sugar beet (for example U. betae),
  • beans for example U. appendiculatus, syn. U. phaseoli
  • sugar beet for example U. betae
  • Ustilago spp. loose smut on cereals (for example U. nuda and U. avaenae), corn (for example U. maydis: corn smut) and sugar cane,
  • Venturia spp. scab
  • apples for example V. inaequalis
  • pears scab
  • Verticillium spp. (leaf and shoot wilt) on various plants, such as fruit trees and ornamental trees, grapevines, soft fruit, vegetable and field crops, such as for example V. dahliae on strawberries, oilseed rape, potatoes and tomatoes.
  • the active compounds and the compositions are suitable for controlling harmful fungi in the protection of materials and buildings (for example wood, paper, paint dispersions, fibers or tissues) and in the protection of stored products.
  • 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., Clado
  • Trichoderma spp. Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of materials the following yeast fungi: Candida spp. and Saccharomyces cerevisae.
  • the active compounds are employed as such or in the form of a fungicidal composition by treating the harmful fungi, their habitat or the plants or plant seed materials to be protected against fungal attack, the soil, areas, materials or spaces with a fungicidally effective amount of the compounds I.
  • the application can be carried out both before and after the infection of the materials, plants or seeds by the fungi.
  • the active compounds can be employed as such, in the form of a composition or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, compositions for broadcasting, granules, by spraying, atomizing, dusting, broadcasting, spreading-on, dipping or watering.
  • the use forms depend entirely on the intended purposes; in each case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the compound(s) I and the compound Il are usually employed in a weight ratio of from 100:1 to 1 :100, preferably from 20:1 to 1 :20, in particular from 10:1 to 1 :10. Any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the compound I.
  • the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 900 g/ha, in particular from 50 to 750 g/ha.
  • the application rates of the compound I are generally from 1 to
  • 1000 g/ha preferably from 10 to 900 g/ha, in particular from 20 to 750 g/ha.
  • the application rates of the active compound Il are generally from 1 to 2000 g/ha, preferably from 10 to 900 g/ha, in particular from 40 to 500 g/ha.
  • the application rates of mixture generally employed are from 1 to 1000 g/100 kg of seed, preferably from 1 to 750 g/100 kg, in particular from 5 to 500 g/100 kg.
  • the application rate of active compound depends on the nature of the area of use and the desired effect.
  • customary application rates are, for example, from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active compound per cubic meter of treated material.
  • plant propagation materials comprises all generative parts of the plant, for example seeds, and vegetative plant parts, such as seedlings and tubers (for example potatoes) which can be used for propagating a plant. They include seeds, roots, fruits, tubers, bulbs, rhizomes, shoots and other parts of plants. Germinated plants and young plants which are transplanted after germination or after emergence are likewise included. The young plants can be protected against harmful fungi by partial or complete treatment, for example by dipping or watering.
  • the treatment of plant propagation material in particular the treatment of seed, is known to the person skilled in the art and is carried out by dusting, coating, pelleting, dipping or drenching of the plant propagation material, the treatment preferably being carried out by pelleting, coating or dusting, such that premature germination, for example, of the seed is prevented.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by addition of water.
  • emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water using wetting agents, tackifiers, dispersants or emulsifiers.
  • wetting agents wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil.
  • the active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1 %.
  • the active compounds can also be employed by the ultra-low volume (ULV) method, where it is possible to apply formulations comprising more than 95% by weight of active compound or even the active compound without additives.
  • UUV ultra-low volume
  • oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides may be added to the active compounds or the compositions comprising them, if appropriate not until immediately prior to use (tank mix).
  • These compositions can be added to the compositions according to the invention in a weight ratio of from 1 :100 to 100:1 , preferably from 1 :10 to 10:1.
  • organically modified polysiloxanes for example Break Thru S 240 ®
  • alcohol alkoxylates for example Atplus ® 245, Atplus ® MBA 1303, Plurafac ® LF 300 and Lutensol ® ON 30
  • EO/PO block polymers for example Pluronic ® RPE 2035 and Genapol ® B
  • alcohol ethoxylates for example Lutensol ® XP 80
  • sodium dioctylsulfosuccinate for example Leophen ® RA.
  • the active compounds were separately or jointly prepared as a stock solution comprising 25 mg of active compound which was made up to 10 ml using a mixture of acetone and/or DMSO and the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio of solvent/emulsifier of 99 to 1. The mixture was then made up with water to 100 ml.
  • Uniperol® EL wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols
  • This stock solution was diluted with the solvent/emulsifier/water mixture described to the concentration of active compound stated below.
  • the efficacy (E) is calculated as follows using Abbot's formula:
  • 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 in DMSO at a concentration of 10 000 ppm.
  • the compounds pyraclostrobin, boscalid, benthiovalicarb, metalaxyl-M and epoxiconazole were used as commercial finished formulations and diluted with water to the stated concentration of the active compound.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of the respective pathogen in a nutrient medium was then added as specified in the respective use example.
  • 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 observed efficacy was calculated using Abbott's formula. An efficacy of 0 means means that the growth level of the pathogens corresponds to that of to the active compound-free control variant; an efficacy of 100 means that the pathogens were not growing.
  • the expected efficacies of active compound combinations were determined using Colby's formula (Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, 20-22, 1967) and compared with the observed efficacies.
  • Use example 2 Activity against the late blight pathogen Phytophthora infestans
  • a spore suspension of Phytophtora infestans in a pea juice-based aqueous nutrient medium was used.
  • a spore suspension of Botrytis cinerea in an aqueous biomalt solution was used.
  • Use example 4 Activity against the rice blast pathogen Pyricularia oryzae
  • a spore suspension of Pyricularia oryzae in an aqueous biomalt solution was used.

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Abstract

The present invention relates to fungicidal mixtures, comprising, as active components, 1 ) at least one 5-hydroxypyrazoline of Formula (I), in which the substituents are defined according to the description, and 2) at least one active compound Il selected from the groups of the azoles, strobilurins, carboxamides, nitrogenous heterocyclyl compounds, carbamates and dithiocarbamates, and other active compounds according to the description in a synergistically effective amount, to methods for controlling harmful fungi using mixtures of a compound I and active compounds Il and to preparations comprising these mixtures, and also to processes for preparing these preparations.

Description

Fungicidal mixtures
Description
The present invention relates to fungicidal mixtures comprising, as active components
1 ) at least one 5-hydroxypyrazoline of the formula I,
Figure imgf000002_0001
in which the substituents have the following meaning:
B is phenyl, naphthyl or 5- or 6-membered hetaryl wherein said hetaryl comprises one to four heteroatoms from the group consisting of O, N and S;
A is C=O, C=S or SO2;
R1 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-alkenyl, C3-Cio-haloalkenyl, C3-Cio-alkynyl or C3-Cio-haloalkynyl,
C3-Cio-cycloalkyl, C3-Cio-cycloalkenyl, Cs-do-cycloalkynyl, phenyl, 5- or 6-membered heterocyclyl or hetaryl wherein said heterocyclyl or hetaryl comprises one to four heteroatoms from the group consisting of O, N and S;
R2 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-halo- alkenyl, C3-Cio-alkynyl, C3-Cio-haloalkynyl, C3-Cio-cycloalkyl, C3-Cio-cyclo- alkenyl, C3-Cio-cycloalkynyl, phenyl, 5- or 6-membered hetaryl or heterocyclyl wherein said hetaryl or heterocyclyl comprises one to four heteroatoms from the group consisting of O, N and S; or together with R1 or
R4 is C3-C4-alkylene or C3-C4-alkenylene,
R3 is hydrogen, nitro, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl,
C2-C4-haloalkynyl or NR'2, where R' independently of one another are hydrogen or Ci-C4-alkyl;
R4 is hydrogen, halogen, nitro, cyano, NR'2, Ci-C4-alkyl, Ci-C4-haloalkyl, COOR', phenyl or 5- or 6-membered hetaryl or heterocyclyl; where the aliphatic chains in R1 and/or R2 may be substituted by one to four identical or different groups Ra:
Ra is halogen, nitro, cyano, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl,
C2-Cio-haloalkenyl, C3-Cio-alkynyl, C3-Cio-haloalkynyl; C3-C10-CVCI0- alkyl, C3-Cio-cycloalkenyl, C3-Cio-cycloalkynyl, aryl, hetaryl, heterocyclyl; COOR', NR'2; where the cyclic groups in R1 and/or Ra and/or R4 may be substituted by one to five groups Rb:
Rb is halogen, cyano, hydroxyl, mercapto, nitro, NR'2, Ci-Cio-alkyl, C-i-Ce-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl or Ci-C6-alkoxy; and
2) at least one active compound Il selected from the following groups:
A) azoles, such as triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triadimefon, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1 ,2,4]triazol-1-yl)- cycloheptanol; imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizole; 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, such as azoxystrobin, dimoxystrobin, enestroburin, fluoxa- strobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, pyribencarb, methyl (2-chloro-5-[1-(3- methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1 -(6- methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate, methyl 2-(ortho- (2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate, 3-methoxy- 2-(2-(N-(4-methoxy-phenyl)-cyclopropane-carboximidoylsulfanylmethyl)- phenyl)-acrylic acid, 2-(2-(6-(3-chloro-2-methyl-phenoxy)-5-fluoro-pyrimidin-
4-yloxy)-phenyl)-2-methoxyimino-N-methyl-acetamide, methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)- 2-methoxyimino-N-methyl-acetamide;
C) carboxanilides: benalaxyl, benalaxyl-M, benodanil, boscalid, carboxin, mepronil, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, metalaxyl, ofurace, oxadixyl, oxycarboxin, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, N-(4'-bromobiphenyl-2-yl)-4- difluoromethyl^-methylthiazole-δ-carboxamide, N-(4'-trifluoromethylbi- phenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4'-chloro- 3'-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(3',4'-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole- 4-carboxamide, N-(2-cyanophenyl)-3,4-dichloroisothiazole-5-carboxamide,
N-(4'-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carbox- amide, N-(4'-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole- 5-carboxamide, N-(4'-chloro-3'-fluorobiphenyl-2-yl)-4-difluoromethyl- 2-methylthiazole-5-carboxamide, N-(3',4'-dichloro-4-fluorobiphenyl-2-yl)- 3-difluoromethyl-1 -methylpyrazole-4-carboxamide, N-(3',4'-dichloro-5-fluo- robiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, 3,4-di- chloro-N-(2-cyanophenyl)isothiazole-5-carboxamide, N-(2',4'-difluorobi- phenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(2',4'-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-car- boxamide, N-(2',4'-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1 H-pyr- azole-4-carboxamide; N-(2',4'-dichlorobiphenyl-2-yl)-3-difluoromethyl- 1 -methyl-1 H-pyrazole-4-carboxamide, N-(2',5'-difluorobiphenyl-2-yl)- 1 -methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(2',5'-dichlorobi- phenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(2',5'-difluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-car- boxamide, N-(2',5'-dichlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyr- azole-4-carboxamide, N-(3',5'-difluorobiphenyl-2-yl)-1-methyl-3-trifluoro- methyl-1 H-pyrazole-4-carboxamide, N-(3',5'-dichlorobiphenyl-2-yl)- 1 -methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(3',5'-difluorobi- phenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide,
N-(3',5'-dichlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole- 4-carboxamide, N-(3'-fluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl- 1 H-pyrazole-4-carboxamide, N-(3'-chlorobiphenyl-2-yl)-1 -methyl-3-trifluoro- methyl-1 H-pyrazole-4-carboxamide, N-(3'-fluorobiphenyl-2-yl)-3-difluoro- methyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(3'-chlorobiphenyl-2-yl)-
3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2'-fluorobi- phenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(2'-chlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carbox- amide; N-(2'-fluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole- 4-carboxamide; N-(2'-chlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-
1 H-pyrazole-4-carboxamide, N-(2'-fluoro-4'-chloro-5'-methylbiphenyl-2-yl)- 1 -methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(3',4',5'-trifluoro- biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide; N-(3',4',5'-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1 H-pyrazole- 4-carboxamide, N-(2',4',5'-trifluorobiphenyl-2-yl)-1 -methyl-3-difluoromethyl-
1 H-pyrazole-4-carboxamide, N-(3',4',5'-trifluorobiphenyl-2-yl)-3-chloro- fluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-[2-(1 ,1 , 2,3,3, 3-hexa- fluoropropoxy)phenyl]-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carbox- amide, N-[2-(1 ,1 ,2,3,3,3-hexafluoropropoxy)phenyl]-3-difluoromethyl- 1 -methyl-1 H-pyrazole-4-carboxamide, N-[2-(2-chloro-1 , 1 ,2-trifluoroethoxy)- phenyl]-1 -methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-[2-(2-chloro-1 ,1 ,2-trifluoroethoxy)phenyl]-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxamide, N-[2-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl]-3-di- fluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-[2-(1 ,1 ,2,2-tetra- fluoroethoxy)phenyl]-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carbox- amide, N-(4'-(trifluoromethylthio)biphenyl-2-yl)-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxamide, N-(4'-(trifluoromethylthio)biphenyl-2-yl)- 1 -methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-[2-(1 ,2-di- methylpropyl)phenyl]-5-fluoro-1 ,3-dimethyl-1 H-pyrazole-4-carboxamide; carboxylic acid morpholides: dimethomorph, flumorph; benzamides: flumetover, fluopicolide (picobenzamid), zoxamide, N-(3-ethyl-3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide; - other carboxamides: carpropamid, diclocymet, mandipropamid, flumetover, oxytetracyclin, silthiofarm, N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]- 3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide, N-(2-{4-[3-(4-chlorophenyl)-prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2- ethanesulfonylamino-3-methylbutyramide;
D) nitrogenous heterocyclyl compounds pyridines: fluazinam, pyrifenox, 3-[5-(4-chlorophenyl)-2,3-dimethylisox- azolidin-3-yl]pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine, 2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyri- dine-2,6-di-carbonitrile, N-(1 -(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4-di- chloronicotinamide, N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloro- nicotinamide; pyrimidines: bupirimate, cyprodinil, diflumetorim, ferimzone, fenarimol, mepanipyrim, nitrapyrin, nuarimol, pyrimethanil; - piperazines: triforine: pyrroles: fludioxonil, fenpiclonil; morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph; - piperidines: fenpropidin; - dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin; non-aromatic 5-membered heterocycles: famoxadone, fenamidone, octhilinone, probenazole,; others: acibenzolar-S-methyl, anilazine, captan, captafol, dazomet, diclomezine, fenoxanil, folpet, fenpropidin, famoxadone, fenamidone, flutianil, octhilinone, probenazole, proquinazid, pyroquilon, quinoxyfen, tricyclazole, δ-amino^-isopropyl-S-oxo^-ortho-tolyl^^-dihydro-pyrazole-i-carbothioic acid S-allyl ester, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluoro- phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine, 6-(3,4-dichlorophenyl)-5-methyl- [1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 6-(4-tert-butylphenyl)-5-methyl- [1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-methyl-6-(3,5,5-trimethylhexyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-methyl-6-octyl-[1 ,2,4]triazolo- [1 ,5-a]pyrimidin-7-ylamine, 6-methyl-5-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin- 7-ylamine, 6-ethyl-5-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-ethyl-
6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-ethyl-6-(3,5,5-trimethyl- hexyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 6-octyl-5-propyl-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidin-7-ylamine, 5-methoxymethyl-6-octyl-[1 ,2,4]triazolo- [1 ,5-a]pyrimidin-7-ylamine, 6-octyl-5-trifluoromethyl-[1 ,2,4]triazolo[1 ,5-a]py- rimidin-7-ylamine and 5-trifluoromethyl-6-(3,5,5-trimethylhexyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidin-7-ylamine, 2-butoxy-6-iodo-3-propylchromene-4-one, N,N-dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1 ,2,4]triazole- 1 -sulfonamide;
E) carbamates and dithiocarbamates dithiocarbamates: ferbam, mancozeb, maneb, metiram, metam, metha- sulphocarb, propineb, thiram, zineb, ziram; carbamates: diethofencarb, benthiavalicarb, iprovalicarb, propamocarb, propamocarb hydrochlorid, valiphenal and (4-fluorophenyl) N-(1-(1-(4- cyanophenyl)ethanesulfonyl)but-2-yl)carbamate; and F) other active compounds guanidines: dodine, dodine free base, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), guazatine, guazatine-acetate; - antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, polyoxins, streptomycin, validamycin A; organometallic compounds: fentin salts; sulfur-containing heterocyclyl compounds: isoprothiolane, dithianon; organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, pyrazophos, tolclofos-methyl, phosphorous acid and its salts; organochlorine compounds: thiophanate-methyl, chlorothalonil, dichlo- fluanid, tolylfluanid, flusulfamide, phthalide, hexachlorobenzene, pencycuron, quintozene; nitrophenyl derivatives: binapacryl, dinocap, dinobuton nitrthal-isopropyl, tecnazen,; inorganic active compounds: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; others: biphenyl, bronopol, spiroxamine, cyflufenamid, cymoxanil, metra- fenone, tolylfluanid, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy- 2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoro- methyl-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-tetra- hydro-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-dimeth- yl-quinolin-4-yl ester; - growth retardants: abscisic acid, amidochlor, ancymidol, 6-benzylamino- purine, brassinolide, butralin, choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole- 3-acetic acid , maleic hydrazide, mefluidide, naphthaleneacetic acid, paclobutrazol, prohexadione and its salts, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid, trinexapac-ethyl, chlormequat, mepiquat-chloride, uniconazole and diflufenzopyr;
in a synergistically effective amount.
Moreover, the invention relates to a method for controlling harmful fungi using mixtures of at least one compound I with active compounds II, and to the use of at least one compound I with active compounds Il for preparing such mixtures, and also to compositions comprising these mixtures.
The 5-hydroxypyrazolines, referred to above as component 1 , of the formula I, their preparation and their action against harmful fungi are known from the literature (WO 2000/20399; WO 2006/128815; WO 2006/128817; WO 2006/128824; WO 2006/128823. The active compounds II, referred to above as component 2 by their common name, their preparation and their action against harmful fungi are generally known (cf.: http://www.hclrss.demon.co.uk/index.html); they are commercially available. The compounds named according to IUPAC, their preparation and their fungicidal action are likewise known: methyl (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1-(6-methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate (EP-A 12 01 648); methyl 2-(ortho-((2,5-dimethylphenyloxymethylene)phenyl)-3-meth- oxyacrylate (EP-A 226 917); 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluoro- phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine (WO 98/46608); 3,4-dichloro-N-(2-cyano- phenyl)isothiazole-5-carboxamide (WO 99/24413); N-(2-{4-[3-(4-chlorophenyl)prop- 2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide, N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethanesulfonyl- amino-3-methylbutyramide (WO 04/049804); N-(4'-bromobiphenyl-2-yl)-4-difluoro- methyl^-methylthiazole-δ-carboxamide, N-(4'-trifluoromethylbiphenyl-2-yl)-4-difluoro- methyl-2-methylthiazole-5-carboxamide, N-(4'-chloro-3'-fluorobiphenyl-2-yl)-4-difluoro- methyl-2-methylthiazole-5-carboxamide, N-(3',4'-dichloro-4-fluorobiphenyl-2-yl)-3-di- fluoromethyl-1-methylpyrazole-4-carboxamide, N-(3',4'-dichloro-5-fluorobiphenyl-2-yl)- S-difluoromethyl-i-methylpyrazole^-carboxamide (WO 03/066609); 2-butoxy-6-iodo- 3-propylchromen-4-one (WO 03/14103); 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin- 3-yl]pyridine (EP-A 10 35 122); amisulbrom, N,N-dimethyl-3-(3-bromo-6-fluoro- 2-methylindole-1-sulfonyl)-[1 ,2,4]triazole-1 -sulfonamide (WO 03/053145); methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)propanoate (EP-A 1028125); 6-(3,4-dichlorophenyl)-5-methyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-yl- amine, 6-(4-tert-butylphenyl)-5-methyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-methyl-6-(3,5,5-trimethyl-hexyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-methyl- 6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 6-methyl-5-octyl-[1 ,2,4]triazolo- [1 ,5-a]pyrimidin-7-ylamine, 6-ethyl-5-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-ethyl-6-(3,5,5-trimethylhexyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 6-octyl-5-propyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin- 7-ylamine, 5-methoxymethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 6-octyl- 5-trifluoromethyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine and 5-trifluoromethyl- 6-(3,5,5-trimethylhexyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine (EP-A 71 792; EP-A 141 317; WO 2003/009687; WO 2005/087771 ; WO 2005/087772;
WO 2005/087773; PCT/EP/05/002426; PCT/EP2006/050922; PCT/EP2006/060399). With a view to reducing the application rates and broadening the activity spectrum of the known compounds, it was an object of the present invention to provide mixtures which, at a reduced total amount of active compounds applied, have improved activity against harmful fungi, in particular for certain indications.
We have found that this object is achieved by the mixtures defined at the outset. Moreover, we have found that simultaneous, that is joint or separate, application of the compounds I and an active compound Il or successive application of the compounds I and an active compound Il allows better control of harmful fungi than is possible with the individual compounds (synergistic mixtures). The compounds I can be used as a synergist for a large number of different active compounds. The simultaneous, that is joint or separate, application of the compound I with an active compound Il increases the fungicidal activity in a superadditive manner.
The mixtures of the compounds I and the active compounds Il are suitable in particular for controlling harmful fungi from the class of the Peronosporomycetes (syn. Oomycetes), such as Peronospora species, Phytophthora species, Plasmopara viticola and Pseudoperonospora species, in particular fungi corresponding to those mentioned above.
In the definitions of the symbols given for the formulae above, collective terms were used which generally represent the following substituents: halogen: fluorine, chlorine, bromine and iodine; alkyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 4, 6, 8 or 10 carbon atoms, for example d-Cε-alkyl, such as methyl, ethyl, propyl, 1 -methyl- ethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 ,1-dimethyl- propyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl- pentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; haloalkyl: straight-chain or branched alkyl groups having 1 to 2, 4 or 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in this groups may be replaced by halogen atoms as mentioned above: in particular Ci-C2-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoro- methyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-tri- fluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1 ,1 ,1-trifluoroprop-2-yl. With a view to the intended use of the hydroxypyrazolines of the formula I, particular preference is given to the following meanings of the substituents, in each case on their own or in combination:
Suitable for the mixtures according to the invention are in particular compounds of the formula I in which B is phenyl which carries a substituent in the 3-position. Moreover, preference is given to compounds I in which B is phenyl which carries a substituent in the 4-position.
Preference is furthermore given to compounds I in which B is phenyl which carries substituents in the 3, 4-position.
In addition, preference is given to compounds I in which the group B is substituted by halogen, such as fluorine, chlorine or bromine, cyano, nitro, hydroxyl, amino, methoxy, Ci-C4-alkyl, such as methyl, ethyl, isopropyl, n-butyl or tert-butyl, in particular methyl or tert-butyl.
A further embodiment of the compounds of the formula I relates to those compounds in which A is C=O.
A further embodiment of the compounds of the formula I relates to those compounds in which A is SO2.
A further embodiment of the compounds of the formula I relates to those compounds in which R1 is Ci-Cio-alkyl or Ci-Cio-haloalkyl. Preference is given to the compounds of the formula I in which R1 is Ci-C4-alkyl, such as methyl, ethyl, isopropyl, n-butyl or tert-butyl.
In addition, preference is also given to the compounds of the formula I in which R1 is Ci-Cβ-haloalkyl, in particular to those groups in which all hydrogen atoms are replaced by halogen atoms, such as chlorine or fluorine, in particular fluorine. Here, R1 is particularly preferably CF3, C2F5, C3F7, C4F9, 2,2,3, 3,4,4,4-heptafluorobutyl or 2,2,3,3,4,4,5,5,5-nonafluoropentyl.
A further embodiment of the compounds of the formula I relates to those compounds in which R1 is phenyl which may be substituted by one to five, in particular one or two, identical or different groups Ra.
A further embodiment of the compounds of the formula I relates to those compounds in which R1 is 5- or 6-membered hetaryl which may be substituted by one to five, in particular one or two, identical or different groups Ra.
A further embodiment of the compounds of the formula I relates to those compounds in which R1 is 5- or 6-membered heterocyclyl which may be substituted by one to five identical or different groups Ra.
A further embodiment of the compounds of the formula I relates to those compounds in which R2 is hydrogen.
A further embodiment of the compounds of the formula I relates to those compounds in which R2 is Ci-C4-alkyl, in particular CH3 or C2H5.
A further embodiment of the compounds of the formula I relates to those compounds in which R1 and R2 together form a C3- or C4-alkylene chain which may be substituted by one or more, in particular one, methyl group.
A further embodiment of the compounds of the formula I relates to those compounds in which R2 and R4 together form a C3- or C4-alkylene chain which may be substituted by one or more, in particular one, methyl group.
A further embodiment of the compounds of the formula I relates to those compounds in which R3 is hydrogen.
A further embodiment of the compounds of the formula I relates to those compounds in which R3 is Ci-C4-alkyl, in particular CH3 or C2H5.
Moreover, preference is given to compounds I in which R4 is hydrogen.
Moreover, preference is given to compounds I in which R4 is Ci-C4-alkyl, such as methyl, ethyl, isopropyl, n-butyl or tert-butyl.
In addition, preference is also given to the compounds of the formula I in which R4 is Ci-Cβ-haloalkyl, in particular to those groups in which all hydrogen atoms are replaced by halogen atoms, such as chlorine or fluorine, in particular fluorine. Here, R4 is particularly preferably CF3, C2F5, C3F7 or C4F9. A further embodiment of the compounds of the formula I relates to those compounds in which R4 is Ci-C4-alkoxycarbonyl, in particular methoxycarbonyl or ethoxycarbonyl.
A further embodiment of the compounds of the formula I relates to those compounds in which R4 is phenyl which may be substituted by one to five, preferably one to four, in particular one or two, identical or different groups Rb.
A further embodiment of the compounds of the formula I relates to those compounds in which R4 is 5- or 6-membered hetaryl which may be substituted by one to five, preferably one to four, in particular one or two, identical or different groups Rb.
Preferred heteraryl groups for the formula I are thienyl, furyl and pyridyl. In particular with a view to their use, preference is given to the compounds I compiled in the tables below. Moreover, the groups mentioned for a substituent in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question. Table 1 : Compounds of the formula I in which A is C=O and R3 is hydrogen and the combination of R1, R2 and R4 for a compound corresponds in each case to one row of table I.
Table 2: Compounds of the formula I in which A is SO2 and R3 is hydrogen and the combination of R1, R2 and R4 for a compound corresponds in each case to one row of table I.
Table I
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
The active compounds can also be used in the form of their agriculturally acceptable salts. Suitable for this purpose are usually alkali metal or alkaline earth metal salts, such as sodium salts, potassium salts or calcium salts. Moreover, the invention relates to agrochemical compositions comprising a fungicidally effective and non-phytotoxic amount of a compound of the formula I, and to their use for controlling harmful fungi.
The term "effective and non-phytotoxic amount" means an amount of the agrochemical composition or the compound which is sufficient for controlling harmful fungi on crop plants and does not cause any significant damage to the crop plants treated. Such an amount may vary over a wide range and depends on numerous factors, such as, for example, the harmful fungus to be controlled, the particular crop plant, the climatic conditions and the compounds.
The compounds I and the active compounds Il can be applied simultaneously, that is jointly or separately, or in succession, the order, in the case of separate application, generally not having any effect on the control results.
The compounds I and the active compounds II, or the mixtures according to the invention, can be converted into the formulations customary for agrochemical/fungicidal compositions, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
The compositions or their formulations are prepared in a known manner, for example by extending the active compounds with solvents and/or carriers, if desired using further auxiliaries such as emulsifiers and dispersants. Here, individual compounds may also have various functions. Solvents, carriers and auxiliaries suitable for this purpose are essentially:
- water, aromatic solvents (for example Solvesso® products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used. - carriers such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example highly disperse silica, silicates); emulsifiers such as nonionogenic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.
The compositions according to the invention can be formulated in solid form or in liquid form. Depending on the embodiment, the compositions according to the invention may also comprise auxiliaries and/or carriers customary in crop protection compositions or in compositions for the protection of materials. The auxiliaries include in particular conventional surface-active substances and other additives and carriers customary in crop protection and in the protection of materials, which compounds may be solid or liquid. The surface-active substances include in particular surfactants, especially those having wetting agent properties. The other auxiliaries (additives) include in particular thickeners, antifoams, preservatives, antifreeze agents, stabilizers, anticaking agents or powder-flow aids and buffers.
Conventional surface-active substances which are suitable in principle are anionic, nonionic and amphoteric surfactants including polymer surfactants, and the molecular weight of the surfactants will typically not exceed a value of 2000 daltons and in particular 1000 daltons (number-average). The anionic surfactants include, for example, carboxylates, in particular alkali metal, alkaline earth metal, and ammonium salts of fatty acids, for example potassium stearate, which are usually also referred to as soaps; acyl glutamates; sarcosinates, for example sodium lauroyl sarcosinate; taurates; methylcelluloses; alkyl phosphates, in particular alkyl esters of mono- and diphosphoric acid; sulfates, in particular alkyl sulfates and alkyl ether sulfates; sulfonates, furthermore alkyl sulfonates and alkylaryl sulfonates, in particular alkali metal, alkaline earth metal and ammonium salts of arylsulfonic acids and of alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acids, such as, for example, lignol and phenolsulfonic acid, naphthalene- and dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonat.es, alkylnaphthalene- sulfonates, alkyl methyl ester sulfonates, condensates of sulfonated naphthalene and derivatives thereof with formaldehyde, condensates of naphthalene sulfonic acids, phenol- and/or phenolsulfonic acids with formaldehyde or with formaldehyde and urea, mono- or dialkyl sulfosuccinates; and also protein hydrolysates and lignosulfite waste liquors. The abovementioned sulfonic acids are advantageously used in the form of their neutral or, if appropriate, basic salts. The nonionic surfactants include, for example, fatty alcohol alkoxylates and oxoalcohol alkoxylates, in particular ethoxylates and propoxylates having degrees of alkoxylation of usually from 2 to 100 and in particular from 3 to 50, for example alkoxylates of Cs-Cso-alkanols or alk(adi)enols, for example of isotridecyl alcohol, lauryl alcohol, oleyl alcohol or stearyl alcohol, and their Ci-C4-alkyl ethers and Ci-C4-alkyl esters, for example their acetates; alkoxylated animal and/or vegetable fats and/or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates, glycerol esters, such as, for example, glycerol monostearate, alkylphenol alkoxylates, such as, for example, ethoxylated isooctylphenol, octylphenol or nonylphenol, tributylphenol polyoxyethylene ether, fatty amine alkoxylates, fatty acid amide alkoxylates and fatty acid diethanolamide alkoxylates, in particular their ethoxylates, sugar surfactants, sorbitol esters, such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, N-alkylgluconamides, alkyl methyl sulfoxides and alkyldimethylphosphine oxides, such as, for example, tetradecyldimethylphosphine oxide.
The amphoteric surfactants include, for example, sulfobetaines, carboxybetaines and alkyldimethylamine oxides, for example tetradecyldimethylamine oxide. Other surfactants which may be mentioned here by way of example are perfluoro surfactants, silicone surfactants, phospholipids, such as, for example, lecithin or chemically modified lecithins, amino acid surfactants, for example N-lauroylglutamate. Suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are 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, for example toluene, xylene, paraffin, tetrahydro- naphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water. Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the compounds I and, if present further active compounds with at least one solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to at least one solid carrier. 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, for example, 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.
In general, the formulations of the compounds according to the invention comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the compounds I. The compounds are preferably employed in a purity of from 90% to 100%, preferably 95% to 100%. For the treatment of seed, the formulations in question give, after two-to-tenfold dilution, active compound concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. The following are examples of formulations:
1. Products for dilution with water
A Water-soluble concentrates (SL, LS)
10 parts by weight of the active compounds are dissolved with 90 parts by weight of water or with a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound dissolves upon dilution with water. This gives a formulation having an active compound content of 10% by weight.
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 added to 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 wetters 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 wetters and made into 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, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight.
H Gel formulations (GF) 20 parts by weight of the active compounds, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or an organic solvent are ground in a ball mill to give a fine suspension. Dilution with water gives a stable suspension with an active compound content of 20% by weight.
2. Products to be applied undiluted
I Dusts (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 with 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 with an active compound content of 0.5% by weight to be applied undiluted. 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 with an active compound content of 10% by weight to be applied undiluted.
Water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF) are usually used for the treatment of plant propagation material, in particular seed. These formulations can be applied to the propagation material in undiluted or, preferably, diluted form. The application can be carried out before sowing.
For seed treatment, preference is given to using suspension formulations. Such formulations usually comprise from 1 to 800 g of active compound/I, from 1 to 200 g of surfactant/I, from 0 to 200 g of antifreeze agent/I, from 0 to 400 g of binder/I, from 0 to 200 g of colorants/l and solvents, preferably water. Further preferred embodiments of the mixtures according to the invention relate to combinations of one of the compounds of table 1 and one of the active compounds Il below: A) azoles
- triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothio- conazole, 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-di- methoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide; B) strobilurins azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, meto- minostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin, 2-(2-(6-(3-chloro-2-methyl-phenoxy)-5-fluoro-pyrimidin-4-yloxy)-phenyl)-2-methoxy- imino-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-di- chlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino- N-methyl-acetamide; C) carboxamides
- carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fen- furam, 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-carbox- anilide, 2-chloro-N-(1 ,1 ,3-trimethyl-indan-4-yl)-nicotinamide, N-(2',4'-difluorobiphe- nyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2',4'-dichlorobi- phenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2',5'-di- fluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2',5'-dichlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carbox- amide, N-(3',5'-difluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-
4-carboxamide, N-(3'-fluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole- 4-carboxamide, N-(3'-chlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole- 4-carboxamide, N-(2'-fluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole- 4-carboxamide, N-(2'-chlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole- 4-carboxamide, N-(3',5'-dichlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyr- azole-4-carboxamide, N-(3',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxamide, N-(2',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl- 1 -methyl-1 H-pyrazole-4-carboxamide, N-[2-(1 ,1 ,2,3,3,3-hexafluoropropoxy)-phenyl]- 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-[2-(1 ,1 ,2,2-tetrafluoro- ethoxy)-phenyl]-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(4'-tri- fluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carbox- amide, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-car- boxamide, N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole- 4-carboxamide, N-(4'-chloro-3',5'-difluoro-biphenyl-2-yl)-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxamide, N-(4'-chloro-3',5'-difluoro-biphenyl-2-yl)-3-trifluoro- methyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(3',4'-dichloro-5'-fluoro-biphenyl- 2-yl)-3-trifluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(3',5'-difluoro- 4'-methyl-biphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(3',5'-difluoro-4'-methyl-biphenyl-2-yl)-3-trifluoromethyl-1 -methyl-1 H-pyrazole- 4-carboxamide, N-[1 ,2,3,4-tetrahydro-9-(1 -methylethyl)-1 ,4-methanonaphthalen-
5-yl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide;
- carboxylic morpholides: dimethomorph, flumorph; benzoic acid amides: flumetover, fluopicolde, 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-pyτidin-3-yl) cyclopropanecarboxylic acid amide;
D) heterocyclic compounds - pyridines: fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyridine-2,6-di-carbo- nitrile, 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-methyl- sulfate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quin- oxyfen, 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-methyl- piperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine, 6-(3,4-di- chloro-phenyl)-5-methyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-(4-tert-butyl- phenyl)-5-methyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 5-methyl-6-(3,5,5-tri- methyl-hexyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 5-methyl-6-octyl-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine-7-ylamine, 6-methyl-5-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-
7-ylamine, 6-ethyl-5-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 5-ethyl-6-octyl- [1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 5-ethyl-6-(3,5,5-trimethyl-hexyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-propyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine- 7-ylamine, 5-methoxymethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-trifluoromethyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine and 5-trifluoro- methyl-6-(3,5,5-trimethyl-hexyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine;
E) carbamates
- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram; - carbamates: benthiavalicarb, diethofencarb, benthiavalicarb, iprovalicarb, propa- mocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
F) other active substances - guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
- antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, poly- oxine, 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, quinto- zene, 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-(cyclo- propylmethoxyimino-(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-trimethyl- silanyl-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-meth- yl-S-trifluoromethyl-pyrazole-i-yO-acety^-piperidin^-ylJ-thiazole^-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide, acetic acid 6-tert.-butyl-8- fluoro-2,3-dimethyl-quinolin-4-yl ester and methoxy-acetic acid 6-tert-butyl-8-fluoro- 2,3-dimethyl-quinolin-4-yl ester.
G) growth regulators abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dike- gulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole; H) herbicides
- acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor; - amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
- aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
- Bipyridyls: diquat, paraquat; - (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;
- cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim; - dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin;
- diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil; - imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;
- phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
- pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate; - pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;
- sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimethoxy- pyrimidin-2-yl)urea; - triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
- ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone,benfluresate, benzofenap, bentazone, benzobicyclon, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethlyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraf I uf en-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, 4-hydroxy-3-[2-(2-methoxy-ethoxymethyl)-6-tri- fluoromethyl-pyridine-3-carbonyl]-bicyclo[3.2.1]oct-3-en-2-one, (3-[2-chloro-4-fluoro- 5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyπmidin-1-yl)-phenoxy]- pyridin-2-yloxy)-acetic acid ethyl ester, θ-amino-δ-chloro^-cyclopropyl-pyπmidine- 4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)- pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro- phenyl)-pyridine-2-carboxylic acid methyl ester. I) insecticides
- organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfen- valerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin; insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etox- azole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
- nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chloro- thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane; - GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-
1 H-pyrazole-3-carbothioic acid amide; macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram;
- mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
- METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon; - Uncouplers: chlorfenapyr;
- oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite;
- moulting disruptor compounds: cryomazine; mixed function oxidase inhibitors: piperonyl butoxide; - sodium channel blockers: indoxacarb, metaflumizone;
- others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, and pyrifluquinazon.
Preference is given to mixtures of a compound of the formula I with at least one active compound selected from the group of the A) azoles.
Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the B) strobilurins.
Preference is given to mixtures of a compound of the formula I with at least one active compound selected from the group of the C) carboxamides.
Preference is furthermore also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the D) heterocyclic compounds.
Preference is furthermore also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the E) carbamates.
Preference is furthermore also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the F) other fungicides.
Preference is furthermore also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the A) azoles selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl, carbendazim and ethaboxam.
Particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the A) azoles selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl and carbendazim. Very particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the A) azoles selected from the group consisting of epoxiconazole, fluquinconazole, flutriafol, metconazole, tebuconazole, triticonazole, prochloraz and carbendazim. Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the B) strobilurins selected from the group consisting of azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin. Particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the B) strobilurins selected from the group consisting of kresoxim-methyl, orysastrobin and pyraclostrobin.
Very particular preference is also given to mixtures of a compound of the formula I with pyraclostrobin. Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the C) carboxamides selected from the group consisting of fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolide (picobenzamid), zoxamide, carpropamid and mandipropamid. Particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the C) carboxamides selected from the group consisting of fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, zoxamide and carpropamid.
Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the D) heterocyclic compounds selected from the group consisting of fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, 5-chloro-7-(4-methyl- piperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine, proquinazid, acibenzolar-S-methyl, captafol, folpet, fenoxanil and quinoxyfen, in particular fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquinazid, acibenzolar-S-methyl, captafol, folpet, fenoxanil and quinoxyfen.
Particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the D) heterocyclic compounds selected from the group consisting of pyrimethanil, dodemorph, fenpropimorph, tridemorph, iprodione, vinclozolin, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluoro- phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine and quinoxyfen, in particular pyrimethanil, dodemorph, fenpropimorph, tridemorph, iprodione, vinclozolin and quinoxyfen. Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the E) carbamates selected from the group consisting of mancozeb, metiram, propineb, thiram, iprovalicarb, flubenthiavalicarb and propamocarb.
Particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the E) carbamates selected from the group consisting of mancozeb and metiram.
Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the F) other fungicides selected from the group consisting of dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl- aluminum, phosphorous acid and its salts, chlorothalonil, dichlofluanid, thiophanate- methyl, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur, cymoxanil, metrafenone and spiroxamine. Particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of the F) other fungicides selected from the group consisting of phosphorous acid and its salts, chlorothalonil and metrafenone.
Preference is also given to three-component mixtures of one compound of the formula I with two of the active compounds Il mentioned above.
The active compounds mentioned in the context of the invention may also be used in the form of their agriculturally acceptable salts. These are usually alkali metal or alkaline earth metal salts, such as sodium salts, potassium salts or calcium salts.
When providing the mixtures, preference is given to using the pure active compounds to which, if required, further active compounds against harmful fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or growth- regulating active compounds or fertilizers may be added as further active components.
In a preferred embodiment of the invention, mixtures of a hydroxypyrazoline and an active compound Il are used. Under certain conditions, it may be advantageous to combine a hydroxypyrazoline with two or more active compounds II. In addition, mixtures of two or more compounds I with one or more active compounds Il may also be suitable.
Suitable further active components in the above sense are in particular the active compounds Il mentioned at the outset and especially the preferred active compounds Il mentioned above. In the case of ternary mixtures, preferred third active components are strobilurins, in particular pyraclostrobin, carboxamides, in particular boscalid, and also organophosphorus compounds, in particular phosphorous acid and its salts.
The compounds I and the active compounds Il can be formulated together, or they can be formulated separately and combined only in the spray liquor (tank mix), immediately prior to application.
The compounds of the formula I and the compositions according to the invention are suitable as fungicides for controlling harmful fungi. They are distinguished by excellent activity against a broad spectrum of phytopathogenic fungi and fungus-like pathogens from the classes of the Plasmodiophoramycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and
Deuteromycetes (syn. Fungi imperfecti). Some of them are systemically active and can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. In addition, they are suitable for controlling fungi and fungus-like pathogens which, inter alia, attack the wood or the roots of crop plants, in particular of grapevines, and also of woody ornamental plants, woody fruit plants and woody forest plants.
They are of particular importance for controlling a large number of fungus pathogens on various crop plants such as cereals, for example wheat, rye, barley, triticale, oats or rice; beets, for example sugar beets or fodder beets; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackcurrant or gooseberries; leguminous plants, for example beans, lentils, peas, lucerne or soybeans; oil plants, for example oilseed rape, mustard, olives, sunflowers, coconuts, cocoa, castor beans, oil palms, peanuts or soybeans; cucurbits, for example pumpkins, cucumbers or melons; fiber plants, for example cotton, flax, hemp or jute; citrus fruits, for example oranges, lemons, grapefruit or mandarins; vegetable plants, for example spinach, lettuce, asparagus, cabbage plants, carrots, onions, tomatoes, potatoes, pumpkins or bell peppers; laurel plants, for example avocados, cinnamon or camphor; energy and raw material plants, for example corn, soybeans, wheat, oilseed rape, sugar cane or oil palms; corn; tobacco; nuts; coffee; tea; bananas; grapevines (table and wine grapes); grass, for example lawn; rubber plants; ornamental and forest plants, for example flowers, shrubs, deciduous trees and coniferous trees, and also on the propagation material, for example seeds, and the harvested material of these plants. The compounds of the formula I and the compositions according to the invention are preferably used for controlling a large number of fungal pathogens in agricultural crops, for example potatoes, sugar beet, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, oilseed rape, leguminous fruits, sunflowers, coffee and sugar cane; fruit, grapevines and ornamental plants and vegetable plants, for example cucumbers, tomatoes, beans and pumpkins.
The term crop plants also includes those which have been modified by breeding, mutagenesis or genetic engineering methods. Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by crossing, mutations or by natural recombination (that is recombination of the genetic information). In general, one or more genes are integrated into the genetic material of the plant in order to improve the properties of the plant.
Thus, the term crop plants also includes those plants which have become tolerant by breeding to herbicide applications (for example applications of bromoxynil or certain herbicide classes, such as HPPD inhibitors, ALS inhibitors, EPSPS inhibitors, glutamine synthetase inhibitors or imidazolinones). Numerous crop plants, for example Clearfield® oilseed rape, which are tolerant to imidazolinones, for example imazamox, have been generated using classical breeding methods (mutagenesis). With the aid of genetic engineering methods, crop plants, such as soy beans, cotton, corn, beets and oilseed rape, resistant to glyphosate and glufosinate have been generated, which are available under the trade names RoundupReady® and Liberty Link®.
Thus, the term crop plants also includes plants which, through genetic engineering, are capable of producing one or more insecticidal proteins, for example those from the bacteria strain Bacillus. These insecticidal proteins bestow upon the plants producing them tolerance to pests from all taxonomic insect classes, in particular to beetles (Coeleropta), dipterans (Diptera) and butterflies (Lepidoptera).
Thus, the term crop plants also includes plants which, through genetic engineering, are capable of producing one or more proteins causing increased resistance to bacterial, viral or fungal pathogens, such as, for example, pathogenesis-related- proteins (PR proteins, see also EP-A 0 392 225), resistance proteins (for example potato cultivars producing two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum) or T4 lysozyme (for example potato cultivars which, by producing this protein, are resistant to bacteria such as Erwinia amylvora).
Thus, the term crop plants also includes plants whose productivity has been improved through genetic engineering, for example by increasing the yield potential (for example biomass, grain yield, starch, oil or protein content), tolerance to drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens.
The term crop plants also includes plants whose ingredients have been modified through genetic engineering in particular for improving human or animal diet, where, for example, oil plants produce health-promoting long-chain omega-3 fatty acids or monounsaturated omega-9 fatty acids (for example Nexera® oilseed rape). The term crop plants also includes plants modified by genetic engineering for improved production of raw materials, for example by increasing the amylopectin content of potatoes.
Specifically, the compounds of the formula I and the compositions according to the invention are suitable for controlling the following plant diseases: Albugo spp. (white rust) on ornamental plants, vegetable crops (for example A.
Candida) and sunflowers (for example A. tragopogonis),
Alternaria spp. (black spot disease, black blotch) on vegetables, oilseed rape (for example A. brassicola or A. brassicae), sugar beet (for example A. tenuis), fruit, rice, soybeans and also on potatoes (for example A. solani or A. alternata) and tomatoes (for example A. solani or A. alternata) and Alternaria spp. (black head) on wheat,
Aphanomyces spp. on sugar beet and vegetables,
Ascochyta spp. on cereals and vegetables, for example A. tritici (leaf blight) on wheat and A. hordei on barley,
Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.) on corn (for example D. maydis), cereals (for example B. sorokiniana: brown leaf spot), rice (for example
B. oryzae) and lawn,
Blumeria (old name: Erysiphe) graminis (powdery mildew) on cereals (for example wheat or barley),
Botryosphaeria spp. ('Black Dead Arm Disease') on grapevines (for example B. obtusa),
Botrytis cinerea (teleomorph: Botryotinia fuckeliana: gray mold, gray rot) on soft fruit and pome fruit (inter alia strawberries), vegetables (inter alia lettuce, carrots, celeriac and cabbage), oilseed rape, flowers, grapevines, forest crops and wheat (ear mold),
Bremia lactucae (downy mildew) on lettuce, Ceratocystis (syn. Ophiostoma) spp. (blue stain fungus) on deciduous trees and coniferous trees, for example C. ulmi (Dutch elm disease) on elms,
Cercospora spp. (Cercospora leaf spot) on corn, rice, sugar beet (for example
C. beticola), sugar cane, vegetables, coffee, soybeans (for example Cercospora sojina or Cercospora kikuchii) and rice,
Cladosporium spp. on tomato (for example C. fulvum: tomato leaf mold) and cereals, for example C. herbarum (ear rot) on wheat,
Claviceps purpurea (ergot) on cereals, Cochliobolus (anamorph: Helminthosporium or Bipolaris) spp. (leaf spot) on corn
(for example C. carbonum), cereals (for example C. sativus, anamorph. Bipolaris sorokiniana: glume blotch) and rice (for example C. miyabeanus, anamorph: H. oryzae),
Colletotrichum (teleomorph: Glomerella) spp. (anthracnosis) on cotton (for example C. gossypii), corn (for example C. graminicola: stem rot and anthracnosis), soft fruit, potatoes (for example C. coccodes: wilt disease), beans (for example C. lindemuthianum) and on soybeans (for example Colletotrichum truncatum), Corticium spp., for example C. sasakii (sheath blight) on rice, Corynespora cassiicola (leaf spot) on soybeans and ornamental plants, Cycloconium spp., for example C. oleaginum on olive,
Cylindrocarpon spp. (for example fruit tree cancer or black foot disease of grapevine, teleomorph: Nectria or Neonectria spp.) on fruit trees, grapevines (for example C. liriodendri, teleomorph: Neonectria liriodendri, black foot disease) and many ornamental trees, Dematophora (teleomorph: Rosellinia) necatrix (root/stem rot) on soybeans,
Diaporthe spp. for example D. phaseolorum (stem disease) on soybeans, Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on com, cereals, such as barley (for example D. teres, net blotch) and on wheat (for example D. tritici-repentis: DTR leaf spot), rice and lawn, esca disease (dieback of grapevine, apoplexia) on grapevines, caused by
Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (old name Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa,
Elsinoe spp. on pome fruit (E. pyri) and soft fruit (E. veneta: anthracnosis) and also grapevines (E. ampelina: anthracnosis), Entyloma oryzae (leaf smut) on rice, Epicoccum spp. (black head) on wheat,
Erysiphe spp. (powdery mildew) on sugar beet (E. betae), vegetables (for example E. pisi), such as cucumber species (for example E. cichoracearum) and cabbage species, such as oilseed rape (for example E. cruciferarum)
Eutypa lata (Eutypa cancer or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees , grapevines and many ornamental trees,
Exserohilum (syn. Helminthosporium) spp. on corn (for example E. turcicum), Fusarium (teleomorph: Gibberella) spp. (wilt disease, root and stem rot) on various plants, such as for example F. graminearum or F. culmorum (root rot and silver-top) on cereals (for example wheat or barley), F. oxysporum on tomatoes, Fusarium solani on soybeans and F. verticillioides on corn,
Gaeumannomyces graminis (take-all) on cereals (for example wheat or barley) and corn,
Gibberella spp. on cereals (for example G. zeae) and rice (for example G. fujikuroi: bakanae disease),
Glomerella cingulata on grapevines, pome fruit and other plants and G. gossypii on cotton,
Grainstaining complex on rice, Guignardia bidwellii (black rot) on grapevines,
Gymnosporangium spp. on Rosaceae and juniper, for example G. sabinae (pear rust) on pears, Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice,
Hemileia spp., for example Hemileia vastatrix (coffee leaf rust) on coffee, lsariopsis clavispora (syn. Cladosporium vitis) on grapevines, Macrophomina phaseolina (syn. phaseoli) (root/stem rot) on soybeans and cotton, Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (for example wheat or barley),
Microsphaera diffusa (powdery mildew) on soybeans,
Monilinia spp., for example M. laxa, M. fructicola and M. fructigena (blossom and twig blight) on stone fruit and other Rosaceae, Mycosphaerella spp. on cereals, bananas, soft fruit and peanuts, such as for example M. graminicola (anamorph: Septoria tritici, Septoria leaf blotch) on wheat or M. fijiensis (sigatoka disease) on bananas,
Peronospora spp. (downy mildew) on cabbage (for example P. brassicae), oilseed rape (for example P. parasitica), bulbous plants (for example P. destructor), tobacco (P. tabacina) and soybeans (for example P. manshurica),
Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans, Phialophora spp. for example on grapevines (for example P. tracheiphila and P. tetraspora) and soybeans (for example P. gregata: stem disease),
Phoma lingam (root and stem rot) on oilseed rape and cabbage and Phoma betae (leaf spot) on sugar beet,
Phomopsis spp. on sunflowers, grapevines (for example P. viticola: dead-arm disease) and soybeans (for example stem canker/stem blight: P. phaseoli, teleomorph: Diaporthe phaseolorum),
Physoderma zeamaydis (brown spot) on corn, Phytophthora spp. (wilt disease, root, leaf, stem and fruit rot) on various plants, such as on bell peppers and cucumber species (for example P. capsici), soybeans (for example P. megasperma, syn. P. sojae), potatoes and tomatoes (for example P. infestans: late blight and brown rot) and deciduous trees (for example P. ramorum: sudden oak death) Plasmodiophora brassicae (club-root) on cabbage, oilseed rape, radish and other plants,
Plasmopara spp., for example P. viticola (peronospora of grapevines, downy mildew) on grapevines and P. halstedii on sunflowers, Podosphaera spp. (powdery mildew) on Rosaceae, hops, pome fruit and soft fruit, for example P. leucotricha on apple,
Polymyxa spp., for example on cereals, such as barley and wheat (P. graminis) and sugar beet (P. betae) and the viral diseases transmitted thereby, Pseudocercosporella herpotrichoides (eyespot/stem break, teleomorph: Tapesia yallundae) on cereals, for example wheat or barley,
Pseudoperonospora (downy mildew) on various plants, for example P. cubensis on cucumber species or P. humili on hops,
Pseudopezicula tracheiphila (angular leaf scorch, anamorph: Phialophora) on grapevines,
Puccinia spp. (rust disease) on various plants, for example P. triticina (brown rust of wheat), P. striiformis (yellow rust), P. hordei (dwarf leaf rust of barley), P. graminis (black rust) or P. recondita (brown rust of rye) on cereals, such as for example wheat, barley or rye, and on asparagus (for example P. asparagi), Pyrenophora tritici-repentis (speckled leaf blotch) on wheat and P. teres (net blotch) on barley,
Pyricularia spp., for example P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on lawn and cereals,
Pythium spp. (damping-off disease) on lawn, rice, corn, wheat, cotton, oilseed rape, sunflowers, sugar beet, vegetables and other plants (for example P. ultimum or P. aphanidermatum),
Ramularia spp., for example R. collo-cygni (Ramularia leaf and awn spot / physiological leaf spot) on barley and R. beticola on sugar beet,
Rhizoctonia spp. on cotton, rice, potatoes, lawn, corn, oilseed rape, potatoes, sugar beet, vegetables and on various other plants, for example R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (sharp eyespot) on wheat or barley,
Rhizopus stolonifer (soft rot) on strawberries, carrots, cabbage and tomato,
Rhynchosporium secalis (leaf spot) on barley, rye and triticale, Sarocladium oryzae and S. attenuatum (sheath rot) on rice,
Sclerotinia spp. on vegetable and field crops, such as oilseed rape, sunflowers (for example Sclerotinia sclerotiorum: stem disease) and soybeans (for example Sclerotinia rolfsii: stem disease),
Septoria spp. on various plants, for example S. glycines (leaf spot) on soybean, S. tritici (Septoria leaf blotch) on wheat and S. (syn. Stagonospora) nodorum (leaf blotch and glume blotch) on cereals,
Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on grapevines,
Setosphaeria spp. (leaf spot) on corn (for example S. turcicum, syn. Helminthosporium turcicum) and lawn,
Sphacelotheca spp. (head smut) on corn, (for example S. reiliana: kernel smut), millet and sugar cane,
Sphaerotheca fuliginea (powdery mildew) on cucumber species, Spongospora subterranea (powdery scab) on potatoes and the viral diseases transmitted thereby,
Stagonospora spp. on cereals, for example S. nodorum (leaf blotch and glume blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat, Synchytrium endobioticum on potatoes (potato wart disease),
Taphrina spp., for example T. deformans (curly-leaf disease) on peach and T. pruni (plum-pocket disease) on plums,
Thielaviopsis spp. (black root rot) on tobacco, pome fruit, vegetable crops, soybeans and cotton, for example T. basicola (syn. Chalara elegans), Tilletia spp. (bunt or stinking smut) on cereals, such as for example T. tritici (syn.
T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat,
Typhula incarnata (gray snow mold) on barley or wheat,
Urocystis spp., for example U. occulta (flag smut) on rye,
Uromyces spp. (rust) on vegetable plants, such as beans (for example U. appendiculatus, syn. U. phaseoli) and sugar beet (for example U. betae),
Ustilago spp. (loose smut) on cereals (for example U. nuda and U. avaenae), corn (for example U. maydis: corn smut) and sugar cane,
Venturia spp. (scab) on apples (for example V. inaequalis) and pears,
Verticillium spp. (leaf and shoot wilt) on various plants, such as fruit trees and ornamental trees, grapevines, soft fruit, vegetable and field crops, such as for example V. dahliae on strawberries, oilseed rape, potatoes and tomatoes.
Moreover, the active compounds and the compositions are suitable for controlling harmful fungi in the protection of materials and buildings (for example wood, paper, paint dispersions, fibers or tissues) and in the protection of stored products. In the protection of wood and buildings, 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.,
Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of materials the following yeast fungi: Candida spp. and Saccharomyces cerevisae.
The active compounds are employed as such or in the form of a fungicidal composition by treating the harmful fungi, their habitat or the plants or plant seed materials to be protected against fungal attack, the soil, areas, materials or spaces with a fungicidally effective amount of the compounds I. The application can be carried out both before and after the infection of the materials, plants or seeds by the fungi.
The active compounds can be employed as such, in the form of a composition or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, compositions for broadcasting, granules, by spraying, atomizing, dusting, broadcasting, spreading-on, dipping or watering. The use forms depend entirely on the intended purposes; in each case, they should ensure the finest possible distribution of the active compounds according to the invention.
The compound(s) I and the compound Il are usually employed in a weight ratio of from 100:1 to 1 :100, preferably from 20:1 to 1 :20, in particular from 10:1 to 1 :10. Any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the compound I.
Depending on the type of compound and the desired effect, the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 900 g/ha, in particular from 50 to 750 g/ha. Correspondingly, the application rates of the compound I are generally from 1 to
1000 g/ha, preferably from 10 to 900 g/ha, in particular from 20 to 750 g/ha.
Correspondingly, the application rates of the active compound Il are generally from 1 to 2000 g/ha, preferably from 10 to 900 g/ha, in particular from 40 to 500 g/ha.
In the treatment of seed, for example by dusting, coating or drenching seed, the application rates of mixture generally employed are from 1 to 1000 g/100 kg of seed, preferably from 1 to 750 g/100 kg, in particular from 5 to 500 g/100 kg.
In the protection of materials and the protection of stored products, the application rate of active compound depends on the nature of the area of use and the desired effect. In the protection of material, customary application rates are, for example, from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active compound per cubic meter of treated material.
The treatment of plant propagation materials, in particular seed, with the mixtures or compositions according to the invention also helps to better protect the user and to preserve the environment. The term plant propagation materials comprises all generative parts of the plant, for example seeds, and vegetative plant parts, such as seedlings and tubers (for example potatoes) which can be used for propagating a plant. They include seeds, roots, fruits, tubers, bulbs, rhizomes, shoots and other parts of plants. Germinated plants and young plants which are transplanted after germination or after emergence are likewise included. The young plants can be protected against harmful fungi by partial or complete treatment, for example by dipping or watering.
The treatment of plant propagation material, in particular the treatment of seed, is known to the person skilled in the art and is carried out by dusting, coating, pelleting, dipping or drenching of the plant propagation material, the treatment preferably being carried out by pelleting, coating or dusting, such that premature germination, for example, of the seed is prevented.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by addition of water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water using wetting agents, tackifiers, dispersants or emulsifiers. However, it is also possible to prepare concentrates suitable for dilution with water and consisting of active substance, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil.
The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1 %.
With good results, the active compounds can also be employed by the ultra-low volume (ULV) method, where it is possible to apply formulations comprising more than 95% by weight of active compound or even the active compound without additives.
Various types of oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides may be added to the active compounds or the compositions comprising them, if appropriate not until immediately prior to use (tank mix). These compositions can be added to the compositions according to the invention in a weight ratio of from 1 :100 to 100:1 , preferably from 1 :10 to 10:1.
The following are particularly suitable as adjuvants in this context: organically modified polysiloxanes, for example Break Thru S 240®; alcohol alkoxylates, for example Atplus® 245, Atplus® MBA 1303, Plurafac® LF 300 and Lutensol® ON 30; EO/PO block polymers, for example Pluronic® RPE 2035 and Genapol® B; alcohol ethoxylates, for example Lutensol® XP 80; and sodium dioctylsulfosuccinate, for example Leophen® RA.
Use examples
The fungicidal effect of the compounds and the mixtures was demonstrated by the following tests:
A) Glass house tests
The active compounds were separately or jointly prepared as a stock solution comprising 25 mg of active compound which was made up to 10 ml using a mixture of acetone and/or DMSO and the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio of solvent/emulsifier of 99 to 1. The mixture was then made up with water to 100 ml.
This stock solution was diluted with the solvent/emulsifier/water mixture described to the concentration of active compound stated below.
Use example 1 - Persistency against late blight on tomatoes caused by Phytophthora infestans
Leaves of potted plants of the cultivar "Great beef tomato St. Pierre" were sprayed to runoff point with an aqueous suspension having the concentration of active compound stated below. After 5 days, the leaves were inoculated with an aqueous spore suspension of Phytophthora infestans. The plants were then placed in a water vapor-saturated chamber at temperatures between 18 and 200C. After 6 days, the late blight on the untreated but infected control plants had developed to such an extent that the infection could be determined visually in %. 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 active compound combinations 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
B) Microtiter tests
The active compounds were formulated separately as a stock solution in DMSO at a concentration of 10 000 ppm. The compounds pyraclostrobin, boscalid, benthiovalicarb, metalaxyl-M and epoxiconazole were used as commercial finished formulations and diluted with water to the stated concentration of the active compound. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the respective pathogen in a nutrient medium was then added as specified in the respective use example. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
The measured parameters were compared to the growth of the active compound-free control variant (= 100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies.The observed efficacy was calculated using Abbott's formula. An efficacy of 0 means means that the growth level of the pathogens corresponds to that of to the active compound-free control variant; an efficacy of 100 means that the pathogens were not growing. The expected efficacies of active compound combinations were determined using Colby's formula (Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, 20-22, 1967) and compared with the observed efficacies. Use example 2: Activity against the late blight pathogen Phytophthora infestans
A spore suspension of Phytophtora infestans in a pea juice-based aqueous nutrient medium was used.
Table II.
Figure imgf000038_0001
Figure imgf000039_0001
n.a. = not applicable
Use example 3: Activity against the grey mold pathogen Botrytis cinerea
A spore suspension of Botrytis cinerea in an aqueous biomalt solution was used.
Table III.
Figure imgf000039_0002
Figure imgf000040_0001
Figure imgf000041_0001
n.a. = not applicable
Use example 4: Activity against the rice blast pathogen Pyricularia oryzae
A spore suspension of Pyricularia oryzae in an aqueous biomalt solution was used.
Table IV.
Figure imgf000041_0002
Figure imgf000042_0001
n.a. = not applicable

Claims

Claims
1. A fungicidal mixture, comprising, as active components:
1 ) at least one 5-hydroxypyrazoline of the formula I ,
Figure imgf000043_0001
in which the substituents have the following meaning: B is phenyl, naphthyl or 5- or 6-membered hetaryl wherein said hetaryl comprises one to four heteroatoms from the group consisting of O, N and S;
A is C=O, C=S or SO2;
R1 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, Cs-do-alkenyl, Cs-do-haloalkenyl, C3-Cio-alkynyl or C3-Cio-haloalkynyl,
C3-Cio-cycloalkyl, C3-Cio-cycloalkenyl, Cs-do-cycloalkynyl, phenyl, 5- or 6-membered heterocyclyl or hetaryl wherein said heterocyclyl or hetaryl comprises one to four heteroatoms from the group consisting of O, N and S; R2 is hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl,
C2-Cio-haloalkenyl, C3-Cio-alkynyl, C3-Cio-haloalkynyl, C3-Cio-cyclo- alkyl, C3-Cio-cycloalkenyl, C3-Cio-cycloalkynyl, phenyl, 5- or 6-membered hetaryl or heterocyclyl wherein said hetaryl or heterocyclyl comprises one to four heteroatoms from the group consisting of O, N and S; or together with R1 or R4 is C3-C4-alkylene or C3-C4- alkenylene,
R3 is hydrogen, nitro, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl or NR'2, where R' independently of one another are hydrogen or Ci-C4-alkyl;
R4 is hydrogen, halogen, nitro, cyano, NR'2, Ci-C4-alkyl, Ci-C4-haloalkyl,
COOR', phenyl or 5- or 6-membered hetaryl or heterocyclyl; where the aliphatic chains in R1 and/or R2 may be substituted by one to four identical or different groups Ra: Ra is halogen, nitro, cyano, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl,
C2-Cio-haloalkenyl, C3-Cio-alkynyl, C3-Cio-haloalkynyl; C3-C10- cycloalkyl, C3-Cio-cycloalkenyl, C3-Cio-cycloalkynyl, aryl, hetaryl, heterocyclyl; COOR', NR'2; where the cyclic groups in R1 and/or Ra and/or R4 may be substituted by one to five groups Rb:
Rb is halogen, cyano, hydroxyl, mercapto, nitro, NR'2, Ci-Cio-alkyl,
C-i-Cε-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl or Ci-Cβ-alkoxy; and
2) at least one active compound Il selected from the following groups:
A) - azoles, such as triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triadimefon, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1 ,2,4]triazol-1-yl)- cycloheptanol; imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizole; 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, such as azoxystrobin, dimoxystrobin, enestroburin, fluoxa- strobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, pyribencarb, methyl (2-chloro-5-[1-(3-methyl- benzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1 -(6-methyl- pyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate, methyl 2-(ortho-(2,5-di- methylphenyloxymethylene)phenyl)-3-methoxyacrylate, 3-methoxy- 2-(2-(N-(4-methoxy-phenyl)-cyclopropane-carboximidoylsulfanylmethyl)- phenyl)-acrylic acid, 2-(2-(6-(3-chloro-2-methyl-phenoxy)-5-fluoro-pyrimidin- 4-yloxy)-phenyl)-2-methoxyimino-N-methyl-acetamide, methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-
2-methoxyimino-N-methyl-acetamide;
C) carboxanilides: benalaxyl, benalaxyl-M, benodanil, boscalid, carboxin, mepronil, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, metalaxyl, ofurace, oxadixyl, oxycarboxin, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, N-(4'-bromobiphenyl-2-yl)-
4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4'-trifluoromethylbi- phenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4'-chloro- 3'-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(3',4'-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole- 4-carboxamide, N-(2-cyanophenyl)-3,4-dichloroisothiazole-5-carboxamide,
N-(4'-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carbox- amide, N-(4'-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole- 5-carboxamide, N-(4'-chloro-3'-fluorobiphenyl-2-yl)-4-difluoromethyl- 2-methylthiazole-5-carboxamide, N-(3',4'-dichloro-4-fluorobiphenyl-2-yl)- 3-difluoromethyl-1-methylpyrazole-4-carboxamide, N-(3',4'-dichloro-5-fluo- robiphenyl-2-yl)-3-difluoromethyl-1 -methylpyrazole-4-carboxamide, 3,4-di- chloro-N-(2-cyanophenyl)isothiazole-5-carboxamide, N-(2',4'-difluorobi- phenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(2',4'-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-car- boxamide, N-(2',4'-difluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyr- azole-4-carboxamide; N-(2',4'-dichlorobiphenyl-2-yl)-3-difluoromethyl-
1 -methyl-1 H-pyrazole-4-carboxamide, N-(2',5'-difluorobiphenyl-2-yl)- 1 -methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(2',5'-dichlorobi- phenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(2',5'-difluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-car- boxamide, N-(2',5'-dichlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyr- azole-4-carboxamide, N-(3',5'-difluorobiphenyl-2-yl)-1-methyl-3-trifluoro- methyl-1 H-pyrazole-4-carboxamide, N-(3',5'-dichlorobiphenyl-2-yl)- 1 -methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(3',5'-difluorobi- phenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(3',5'-dichlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-
4-carboxamide, N-(3'-fluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl- 1 H-pyrazole-4-carboxamide, N-(3'-chlorobiphenyl-2-yl)-1 -methyl-3-trifluoro- methyl-1 H-pyrazole-4-carboxamide, N-(3'-fluorobiphenyl-2-yl)-3-difluoro- methyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(3'-chlorobiphenyl-2-yl)- 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2'-fluorobi- phenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(2'-chlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carbox- amide; N-(2'-fluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole- 4-carboxamide; N-(2'-chlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxamide, N-(2'-fluoro-4'-chloro-5'-methylbiphenyl-2-yl)-
1 -methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-(3',4',5'-trifluoro- biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide; N-(3',4',5'-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1 H-pyrazole- 4-carboxamide, N-(2',4',5'-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl- 1 H-pyrazole-4-carboxamide, N-(3',4',5'-trifluorobiphenyl-2-yl)-3-chloro- fluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-[2-(1 ,1 , 2,3,3, 3-hexa- fluoropropoxy)phenyl]-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carbox- amide, N-[2-(1 ,1 , 2,3,3, 3-hexafluoropropoxy)phenyl]-3-difluoromethyl- 1 -methyl-1 H-pyrazole-4-carboxamide, N-[2-(2-chloro-1 , 1 ,2-trifluoroethoxy)- phenyl]-1 -methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide,
N-[2-(2-chloro-1 ,1 ,2-trifluoroethoxy)phenyl]-3-difluoromethyl-1 -methyl- 1 H-pyrazole-4-carboxamide, N-[2-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl]-3-di- fluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide, N-[2-(1 ,1 ,2,2-tetra- fluoroethoxy)phenyl]-1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carbox- amide, N-(4'-(trifluoromethylthio)biphenyl-2-yl)-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxamide, N-(4'-(trifluoromethylthio)biphenyl-2-yl)-
1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxamide, N-[2-(1 ,2-di- methylpropyl)phenyl]-5-fluoro-1 ,3-dimethyl-1 H-pyrazole-4-carboxamide; carboxylic acid morpholides: dimethomorph, flumorph; benzamides: flumetover, fluopicolide (picobenzamid), zoxamide, N-(3-ethyl-3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide; other carboxamides: carpropamid, diclocymet, mandipropamid, flumetover, oxytetracyclin, silthiofarm, N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]- 3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide, N-(2-{4-[3-(4-chlorophenyl)-prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2- ethanesulfonylamino-3-methylbutyramide;
D) nitrogenous heterocyclyl compounds pyridines: fluazinam, pyrifenox, 3-[5-(4-chlorophenyl)-2,3-dimethylisox- azolidin-3-yl]pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine, 2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyri- dine-2,6-di-carbonitrile, N-(1 -(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4-di- chloronicotinamide, N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloro- nicotinamide; pyrimidines: bupirimate, cyprodinil, diflumetorim, ferimzone, fenarimol, mepanipyrim, nitrapyrin, nuarimol, pyrimethanil; - piperazines: triforine; pyrroles: fludioxonil, fenpiclonil; morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph; piperidines: fenpropidin; - dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin; non-aromatic 5-membered heterocycles: famoxadone, fenamidone, octhilinone, probenazole,; others: acibenzolar-S-methyl, anilazine, captan, captafol, dazomet, diclo- mezine, fenoxanil, folpet, fenpropidin, famoxadone, fenamidone, flutianil, octhilinone, probenazole, proquinazid, pyroquilon, quinoxyfen, tricyclazole, δ-amino^-isopropyl-S-oxo^-ortho-tolyl^^-dihydro-pyrazole-i-carbothioic acid S-allyl ester, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluoro- phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine, 6-(3,4-dichlorophenyl)-5-methyl- [1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 6-(4-tert-butylphenyl)-5-methyl- [1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-methyl-6-(3,5,5-trimethylhexyl)-
[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-methyl-6-octyl-[1 ,2,4]triazolo- [1 ,5-a]pyτimidin-7-ylamine, 6-methyl-5-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin- 7-ylamine, 6-ethyl-5-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-ethyl- 6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, 5-ethyl-6-(3,5,5-trimethyl- hexyl)-[1 ,2,4]triazolo[1 ,5-a]pyτimidin-7-ylamine, 6-octyl-5-propyl-[1 ,2,4]tri- azolo[1 ,5-a]pyτimidin-7-ylamine, 5-methoxymethyl-6-octyl-[1 ,2,4]triazolo-
[1 ,5-a]pyrimidin-7-ylamine, 6-octyl-5-trifluoromethyl-[1 ,2,4]triazolo[1 ,5-a]py- rimidin-7-ylamine and 5-trifluoromethyl-6-(3,5,5-trimethylhexyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidin-7-ylamine, 2-butoxy-6-iodo-3-propylchromene-4-one, N,N-dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1 ,2,4]triazole- 1 -sulfonamide;
E) carbamates and dithiocarbamates dithiocarbamates: ferbam, mancozeb, maneb, metiram, metam, metha- sulphocarb, propineb, thiram, zineb, ziram; carbamates: diethofencarb, benthiavalicarb, iprovalicarb, propamocarb, propamocarb hydrochlorid, valiphenal, (4-fluorophenyl) N-(1-(1-(4-cyano- phenyl)ethanesulfonyl)but-2-yl)carbamate; and
F) other active compounds guanidines: dodine, dodine free base, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), guazatine, guazatine-acetate; antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, polyoxins, streptomycin, validamycin A; organometallic compounds: fentin salts; sulfur-containing heterocyclyl compounds: isoprothiolane, dithianon; - organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, pyrazophos, tolclofos-methyl, phosphorous acid and its salts; organochlorine compounds: thiophanate-methyl, chlorothalonil, dichlo- fluanid, tolylfluanid, flusulfamide, phthalide, hexachlorobenzene, pencycuron, quintozene; - nitrophenyl derivatives: binapacryl, dinocap, dinobuton nitrthal-isopropyl, tecnazen,; inorganic active compounds: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; others: biphenyl, bronopol, spiroxamine, cyflufenamid, cymoxanil, metra- fenone, tolylfluanid, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-
2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoro- methyl-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-tetra- hydro-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-dimeth- yl-quinolin-4-yl ester; growth retardants: abscisic acid, amidochlor, ancymidol, 6-benzylamino- purine, brassinolide, butralin, choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole- 3-acetic acid , maleic hydrazide, mefluidide, naphthaleneacetic acid, paclobutrazol, prohexadione and its salts, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid, trinexapac-ethyl, chlormequat, mepiquat-chloride, uniconazole and diflufenzopyr; in a synergistically effective amount.
2. A fungicidal mixture according to claim 1 , comprising a compound of the formula I and an active compound Il in a weight ratio of from 100:1 to 1 :100.
3. A fungicidal mixture according to claim 1 or 2, comprising a further active compound.
4. An agrochemical composition, comprising a liquid or solid carrier and a mixture according to any of claims 1 to 3.
5. A method for controlling phytopathogenic harmful fungi which comprises treating the fungi, their habitat or the plants, the soil or seed to be protected against fungal attack with a synergistically effective amount of a compound I and an active compound Il according to claim 1.
6. The method according to claim 5, wherein the compounds I and Il according to claim 1 are applied simultaneously, that is jointly or separately, or in succession.
7. The method according to any of claims 5, 6 and 7, wherein the compounds I and Il according to claim 1 or the mixture according to any of claims 1 to 4 are/is applied in an amount of from 5 g/ha to 2000 g/ha.
8. The method according to any of claims 5, 6 and 7, wherein the compounds I and Il according to claim 1 or the mixture according to any of claims 1 to 3 are/is applied in an amount of from 1 to 1000 g/100 kg of seed.
9. Seed, comprising a mixture according to any of claims 1 to 3 in an amount of from 1 to 1000 g/100 kg.
10. A process for preparing a composition according to claim 4, wherein a compound of the formula I and an active compound Il according to claim 1 are extended with solvents and/or carriers.
PCT/EP2008/065764 2007-11-20 2008-11-18 Fungicidal mixtures WO2009065834A2 (en)

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CN101984819A (en) * 2010-07-15 2011-03-16 江阴苏利科技有限公司 Sterilization composition containing fluazinam and difenoconazole and application thereof
CN102308813A (en) * 2011-04-23 2012-01-11 陕西韦尔奇作物保护有限公司 Germicide composition containing spiroxamine and tridemorph
CN102334503A (en) * 2010-07-23 2012-02-01 青岛奥迪斯生物科技有限公司 High efficiency sterilization composition containing mancozeb and flusilazole
CN104430441A (en) * 2014-12-20 2015-03-25 唐睿 Formula and preparation method of water dispersible granules containing propineb and cymoxanil

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WO2006128824A1 (en) * 2005-05-31 2006-12-07 Basf Aktiengesellschaft Fungicidal 5-hydroxypyrazolines, method for the production thereof, and agents containing the same
EP1813151A1 (en) * 2006-01-26 2007-08-01 BASF Aktiengesellschaft Fungicidal compositions based on 1-methyl-pyrazol-4-yl-anilides

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Publication number Priority date Publication date Assignee Title
CN101642112A (en) * 2009-09-08 2010-02-10 深圳诺普信农化股份有限公司 Bactericidal composition containing tetraconazole and application thereof
CN101642112B (en) * 2009-09-08 2012-09-12 深圳诺普信农化股份有限公司 Bactericidal composition containing tetraconazole and application thereof
CN101984819A (en) * 2010-07-15 2011-03-16 江阴苏利科技有限公司 Sterilization composition containing fluazinam and difenoconazole and application thereof
CN102334503A (en) * 2010-07-23 2012-02-01 青岛奥迪斯生物科技有限公司 High efficiency sterilization composition containing mancozeb and flusilazole
CN102308813A (en) * 2011-04-23 2012-01-11 陕西韦尔奇作物保护有限公司 Germicide composition containing spiroxamine and tridemorph
CN102308813B (en) * 2011-04-23 2014-04-02 陕西韦尔奇作物保护有限公司 Germicide composition containing spiroxamine and tridemorph
CN104430441A (en) * 2014-12-20 2015-03-25 唐睿 Formula and preparation method of water dispersible granules containing propineb and cymoxanil

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