WO2007003564A1 - Fungicide mixtures based on 3,5-disubstituted pyrazol-carboxylic acid biphenylamides - Google Patents

Fungicide mixtures based on 3,5-disubstituted pyrazol-carboxylic acid biphenylamides Download PDF

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Publication number
WO2007003564A1
WO2007003564A1 PCT/EP2006/063664 EP2006063664W WO2007003564A1 WO 2007003564 A1 WO2007003564 A1 WO 2007003564A1 EP 2006063664 W EP2006063664 W EP 2006063664W WO 2007003564 A1 WO2007003564 A1 WO 2007003564A1
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Prior art keywords
methyl
carboxylic acid
amide
pyrazole
chloro
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PCT/EP2006/063664
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German (de)
French (fr)
Inventor
Jochen Dietz
Markus Gewehr
Siegfried Strathmann
Reinhard Stierl
Frank Werner
Maria Scherer
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Basf Aktiengesellschaft
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to US11/988,141 priority Critical patent/US20090042725A1/en
Priority to JP2008518845A priority patent/JP2009500311A/en
Priority to BRPI0612804A priority patent/BRPI0612804A2/en
Priority to EP06763960A priority patent/EP1903867A1/en
Publication of WO2007003564A1 publication Critical patent/WO2007003564A1/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 1) at least one 3,5-disubstituted pyrazolecarboxylic acid biphenylamide of the formula I.
  • R 1 and R 2 independently of one another are cyano, nitro, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -
  • Haloalkyl methoxy, difluoromethoxy or trifluoromethoxy
  • R 3 is halogen, -C 4 -alkyl or Ci-C 4 haloalkyl
  • R 4 is hydrogen or halogen
  • Azoles selected from bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, triadimefon , Triadimol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamide, benomyl, carbendazim, thiadanazole, fuberidazole, ethaboxam, etridiazole and hymexazole
  • Carboxylic acid amides selected from carboxin, benalaxyl, boscalid, fenhexamid, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, 3,4-dichloro-N- (2) cyanopheny O-isothiazole- ⁇ -carboxamide, dimethomorph, flumorph, fl uidover, fluopicolide (picobenzamide), zoxamide, carpropamide, diclocymet, mandipropamide, N- (2- [4- [3- (4-chloro-phenyl) -propyl] 2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino-3-methylbutyrannide
  • R 5 is methyl or ethyl
  • Heterocyclic compounds selected from fluazinam, pyrifenox, bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil, triforin, fenpiclonil, fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone, vinclozolin, family oxadone, fenamidone, octhilinone, probenazole, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1 , 5-a] pyrimidine, anilazine, diclomethine, pyroquilone, proquinazide, tricyclazole, the compound of formula IV (2-butoxy-6-iodo-3
  • Z is N or CH
  • fungicides selected from guanidines: dodin, iminoctadine, guazatine, antibiotics: kasugamycin, streptomycin, polyoxin, validamycin A, nitrophenyl derivatives: binapacryl, dinocap, dinobuton,
  • Sulfur-containing heterocyclyl compounds dithianone, isoprothiolane, organometallic compounds: fentin salts, such as fentin acetate, organophosphorus compounds: edifenphos, Iprobenfos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, toiolo-fos-methyl,
  • Organochlorine Compounds Chlorothalonil, Dichlofluanid, Flusulfamide, Hexachlorobenzene, Phthalide, Pencycuron, Quintozen, Thiophanate-Methyl, Toiylfluanide,
  • Inorganic active ingredients Bordeaux broth, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur,
  • Cyflufenamid Cymoxanil, Dimethirimol, Ethirimol, Furalaxyl, Metrafenone and Spiroxamine;
  • the invention relates to a method for controlling harmful fungi with the mixture of at least one compound I and at least one of the active compounds II, the use of the compounds I and II for the preparation of such mixtures and agents and seeds containing these mixtures.
  • Substituted biphenylamides of the formula I are known from EP-A 589 301, in which a process for their preparation and a list of possible mixing partners from the series of fungicides, bactericides, acaricides, nematicides or insecticides is given.
  • WO 01/42223 likewise discloses substituted biphenylamides which, however, are only monosubstituted on the biphenyl radical.
  • 2,4-Disubstituted biphenylamides are known from WO 2005/123689 and WO 2005/123690, and 3,5-disubstituted biphenylamides are known from the earlier German Application No. 102005007160.0.
  • the active compounds II mentioned above as component 2), their preparation and their action against harmful fungi are generally known (cf., for example, http://www.hclrss.demon.co.uk/index.html); they are commercially available.
  • Spiroxamine (8-tert-butyl-1,4-dioxaspiro [4.5] dec-2-yl) diethylamine (EP-A 281 842);
  • Tridemorph, 2,6-dimethyl-4-tridecylmorpholine (DE-A 11 64 152);
  • Mepanipyrim (4-methyl-6-prop-1-ynyl-pyrimidin-2-yl) -phenylamine (EP-A 224 339); Cyprodinil, (4-cyclopropyl-6-methylpyrimidin-2-yl) -phenylamine (EP-A 310550);
  • Difenoconazole 1 - ⁇ 2- [2-chloro-4- (4-chlorophenoxy) phenyl] -4-methyl- [1,3-dioxolan-2-ylmethyl ⁇ -1 H- [1,2,4] triazole ( GB-A 2 098 607); Diniconazole, ( ⁇ E) - ⁇ - [(2,4-dichlorophenyl) methylene] - ⁇ - (1, 1-dimethylethyl) -1H-1, 2,4-triazole-1-ethanol (Noyaku Kagaku, 1983, Vol 8, p. 575);
  • Ipconazole 2 - [(4-chlorophenyl) methyl] -5- (1-methylethyl) -1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (EP-A 267,778); Metconazole, 5- (4-chlorobenzyl) -2,2-dimethyl-1 - [1, 2,4] triazole-1-ylmethylcyclopentanol
  • Penconazole 1- [2- (2,4-dichlorophenyl) pentyl] -1 H- [1,2,4] triazole (Pesticide Manual, 12th Edition 2000, p. 712);
  • Tetraconazole 1 - [2- (2,4-dichlorophenyl) -3- (1,1,2,2-tetrafluoroethoxy) propyl] -1H-1, 2,4-triazole (EP-A 234 242);
  • Triflumizole (4-chloro-2-trifluoromethylphenyl) - (2-propoxy-1 - [1, 2,4] triazole-1-yl-ethylidene) -amine (JP-A 79/119 462);
  • Metiram zinc ammonium ethylenebis (dithiocarbamate) (US 3,248,400); Propineb, zinc propylene bis (dithiocarbamate) polymer (BE 611 960);
  • Carbendazim (1 H-benzimidazol-2-yl) -carbamic acid methyl ester (US 3,657,443); Carboxin, 5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-carboxamide (US 3,249,499);
  • Cyazofamide 4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazole-1-sulfonamide (CAS RN 120116-88-3]; dazomet, 3,5-dimethyl- 1, 3,5-thiadiazinan-2-thione (Bull. Soc. Chim. Fr. Vol. 15, p. 891
  • Furametpyr 5-chloro-N- (1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl) -1,3-dimethyl-1H-pyrazole-4-carboxamide [CAS RN 123572-88-3 ]; Isoprothiolane, diisopropyl 1, 3-dithiolan-2-ylidenmalonate (Proc. Insectic. Fungic. Conf.
  • Tricyclazole 5-methyl-1,2,4-triazolo [3,4-b] [1,3] benzothiazole [CAS RN 41814-78-2];
  • Nitrothal isopropyl, diisopropyl 5-nitroisophthalate Proc. Br. Insectic. Fungic. Conf.
  • Chlorothalonil, 2,4,5,6-tetrachloroisophthalonitrile (US 3,290,353);
  • Fosetyl Fosetyl Aluminum, Ethyl Phosphonate (FR 22 54 276); Iprovalicarb, [(1S) -2-methyl-1- (1-p-tolyl-ethylcarbamoyl) -propyl] -carbamic acid isopropyl ester (EP-A 472 996);
  • Penthiopyrad (RS) -N- [2- (1, 3-dimethylbutyl) -3-thienyl] -1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxamide (JP 10/130268);
  • Pyraclostrobin N- ⁇ 2- [1- (4-chlorophenyl) -1H-pyrazol-3-yloxymethyl] phenyl ⁇ (N-methoxy) carbamic acid, n-methyl ester (WO 96/01256); Trifloxystrobin, methyl (E) -methoxyimino ⁇ (E) - ⁇ - [1- ( ⁇ , ⁇ , ⁇ -trifluoro-m-tolyl) ethylideneaminooxy] -o-tolyl ⁇ acetate (EP-A 460 575);
  • the present invention was based on mixtures which have an improved action against harmful fungi, in particular for certain indications, with a reduced total amount of active substances applied.
  • the compounds I can be used as synergists for a variety of different fungicidal agents.
  • the fungicidal activity is increased to a superadditive extent.
  • halogen is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
  • C 1 -C 4 -alkyl is methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl, preferably methyl or ethyl.
  • Ci-C ⁇ -alkyl is a Ci-C 4 -alkyl radical as mentioned above, or for n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1 - methylpropyl and 1-ethyl-2-methyl-propyl, preferably a Ci-C 4 -
  • Ci-C 4 haloalkyl is a partially or completely halogenated Ci-C 4 alkyl rest, wherein the / the halogen atom (s), especially fluorine, chlorine and / or bromine is / are eg chloromethyl, bromomethyl, dichloromethyl, Trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloroethyl 2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethy
  • C 1 -C 6 -haloalkyl represents a partially or completely halogenated C 1 -C 6 -alkyl radical, where the halogen atom (s) is, in particular, fluorine, chlorine and / or bromine, ie, for example, a C 1 -C 4 -haloalkyl radical as mentioned above, or for 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, 5,5,5-trichloropentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6- lodhexyl, 6,6,6-trichlorohexyl or Dodecafluorhexyl, preferably a Ci-C 4 haloalkyl group.
  • Those compounds I in which X is sulfur can be prepared, for example, by sulfurization of the corresponding compounds I in which X is oxygen (cf., for example, D. Petrova & K. Jakobcic, Croat. Chem. Acta 48, 49 (1976 ) and WO 01/42223).
  • X is oxygen
  • those in which X is oxygen are preferred.
  • R 1 and R 2 are independently cyano, fluorine, chlorine, methyl, methoxy or trifluoromethyl
  • R 3 is fluorine, chlorine, methyl or Ci-haloalkyl
  • R 4 is hydrogen or halogen.
  • R 1 and R 2 independently of one another are cyano, fluorine, chlorine or methoxy and R 3 is fluorine, chlorine, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl and R 3 4 represent hydrogen, fluorine or chlorine.
  • R 1 and R 2 independently of one another, are fluorine or chlorine
  • R 3 is methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl
  • R 4 is hydrogen
  • Very particularly preferred compounds of the formula I are 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'-dichlorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl 1-H-pyrazole-4-carboxylic acid N- (3 ', 5'-difluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro-5'-fluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'-bis (trifluoromethyl) biphenyl-2 -yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'-dichlorobiphenyl-2-yl) -amide, 1-
  • mixtures of a compound of the formula I with at least one active compound selected from the group of the D) heterocyclic compounds are also preferred.
  • mixtures of a compound of formula I with at least one active ingredient selected from the group of E) carbamates are also preferred.
  • mixtures of a compound of formula I with at least one active ingredient selected from the group of F) other fungicides are also preferred.
  • active compound selected from the group of A) azoles selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propi
  • A) azoles selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, propiconazole, prothioconazole, triadimefon, triadimenol, tebucon
  • active substance selected from the group of A) azoles selected from epoxiconazole, fluquinconazole, flutriafol, metconazole, tebuconazole, triticonazole, prochloraz and carbendazim.
  • B) strobilurins selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclobutin 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 consisting of B) strobilurins selected from kresoxim-methyl, orysastrobin and pyraclostrobin.
  • active compound selected from the group consisting of d) heterocyclic compounds selected from pyrimethanil, dodemorph, fenpropimorph, tridemorph, iprodione, vinclozoline, 5-chloro-7- (4-methyl) piperidin-1-yl) -6- (2,4,6-trifluorophenyl)
  • active compound selected from the group consisting of E) carbamates selected from 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 E) carbamates selected from mancozeb and metiram.
  • active compound selected from the group of F fungicides selected from dithianone, fentin salts such as fentin acetate, fosetyl, fosetyl aluminum, phosphorous acid and their salts, chlorothalonil, dichlofluanide , Thiophanate-methyl, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur, cymox
  • Other fungicides selected from phosphorous acid and its salts, chlorothalonil and metrafenone.
  • the mixtures of compound (s) I and at least one of the active compounds II, or the simultaneous joint or separate use of at least one compound I with at least one of the active compounds II, are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Basidiomycetes, Peronospo- romyceten (syn. Oomycetes). They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides. They can also be used for seed treatment.
  • Alternaria species on vegetables, rapeseed, sugar beets and fruits and rice e.g. A. solani or A. alternata on potatoes and tomatoes, - Aphanomyces species on sugar beet and vegetables,
  • Drechslera species Pyrenophora species on corn, cereals, rice and turf, e.g. D. teres to barley or D. tritici-repentis to wheat,
  • Fusarium and Verticillium species on various plants e.g. F. graminearum or F. culmorum on cereal or F. oxysporum on a variety of plants, e.g. Tomatoes,
  • Gibberella species on cereals and rice e.g., Gibberella fujikuroi on rice
  • Mycosphaerella species on cereals, bananas and peanuts e.g. M. graminicola on wheat or M. fijiesis on bananas,
  • Peronospora species on cabbage and bulbous plants e.g. P. brassicae on cabbage or P. destructor on onion, - Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans,
  • Phytophthora species on various plants e.g. P. capsici on paprika
  • Pseudoperonospora on various plants e.g. P. cubensis on cucumber or
  • Puccinia species on various plants e.g. P. triticina, P. striformins, P. hordei or P. graminis on cereals or P. asparagi on asparagus,
  • Rhizoctonia species on cotton, rice, potatoes, turf, corn, rapeseed, sugar beets, vegetables and on various plants e.g. R. solani on beets and various plants, - Rhynchosporium secalis on barley, rye and triticale,
  • Ustilago species on cereals, maize and sugarcane e.g. U. maydis on corn
  • Venturia species (scab) on apples and pears e.g. V. inaequalis to apple.
  • mixtures according to the invention are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions,
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriela spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophlum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Tyromyces spp. Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderm spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.
  • the mixtures are applied by treating the fungi or the plants, seeds, materials or soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients.
  • the application can be done both before and after the infection of the materials, plants or seeds by the fungi.
  • the compound (s) I with at least one of the active ingredients II can be applied simultaneously, namely jointly or separately, or in succession, the sequence in the case of separate application generally having no effect on the control result.
  • the pure active substances I to II are preferably used in the preparation of the mixtures, to which other active substances can be added against harmful fungi or against other pests such as insects, spider animals or nematodes or else herbicidal or growth-regulating active substances or fertilizers.
  • Such mixtures of three active substances consist of a mixture of a compound of formula I, particularly 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid-N- (3 ', 5 1 - difluorobiphenyl-2-yl) -amide, 1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5 1 -dichlorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4 carboxylic acid-N- (3 ', 5 1 - difluorobiphenyl-2-yl) amide or 1-methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid-N- (S'. ⁇ '-dichlorobiphenyl ⁇ -y ⁇ amide, an azole from group A), in particular epoxiconazole, metconazole, triticonazole or fluquinconazole, and
  • mixtures of at least one compound I and at least one active ingredient II are used.
  • mixtures of at least one compound I with two or, if desired, several active components can also offer particular advantages.
  • Suitable further active components in the above sense are, in particular, the aforementioned active compounds II and in particular the above-mentioned preferred active compounds II.
  • Compound (s) I and active compound (II) II are usually used 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.
  • the further active components are mixed in a ratio of from 20: 1 to 1:20 to give compound I.
  • the application rates of the mixtures according to the invention at 5 g / ha to 2000 g / ha, preferably 20 to 1500 g / ha, in particular 50 to 1000 g /Ha.
  • the application rates for the compound (s) I are accordingly generally 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 20 to 750 g / ha.
  • the application rates for the active ingredients II are correspondingly generally 1 to 2000 g / ha, preferably 1 to 1500 g / ha, in particular 40 to 1000 g / ha.
  • application rates of mixture of 1 to 1000 g per 100 kg of seed, preferably 1 to 750 g per 100 kg, in particular 5 to 500 g per 100 kg of seed are generally used.
  • the method for controlling harmful fungi is carried out by the separate or combined application of compound (s) I and at least one of the active compounds II, or a mixture of compound (s) I and at least one of the active ingredients II, by spraying or dusting the seeds, the Plants or soils before or after sowing the plants or before or after emergence of the plants.
  • the fungicidal synergistic mixtures according to the invention can be converted into the customary formulations.
  • be transferred for example, solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the application form depends on the respective purpose; It should in any case ensure the finest possible and uniform distribution of the mixture according to the invention.
  • the formulations are prepared in a manner known per se, for example by stretching the active compounds with solvents and / or excipients, if desired using emulsifiers and dispersants.
  • Solvents / auxiliary materials which are suitable are essentially: - water, aromatic solvents (for example Solvesso ® products, xylene), paraffins
  • solvent mixtures can also be used.
  • alcohols eg, methanol, butanol, pentanol, benzyl alcohol
  • ketones eg, cyclohexanone, gamma-butyrolactone
  • pyrrolidones N-methylpyrrolidone, N-octylpyrrolidone
  • acetates glycols, dimethyl fatty acid amides , Fatty acids and fatty acid esters.
  • solvent mixtures can also be used.
  • Carriers such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.
  • ground natural minerals e.g., kaolins, clays, talc, chalk
  • ground synthetic minerals e.g., fumed silica, silicates
  • Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.
  • the surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl
  • emulsions, pastes or oil dispersions come mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg toluene, xylene, paraffin, Tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.
  • Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with at least one solid carrier.
  • Granules e.g. Coated, impregnated or homogeneous granules may be prepared by binding the active ingredients to at least one solid carrier.
  • Solid carriers are, for example, mineral soils such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the formulations generally contain from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the compound (s) I and at least one of the active compounds II or of the mixture of compound (I) I with at least one of the active ingredients II.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR or HPLC spectrum).
  • formulations are: 1. Products for dilution in water
  • DC Dispersible Concentrates 20 parts by weight of a mixture according to the invention are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersing agent, e.g. Polyvinylpyrrolidone, dissolved. Dilution in water gives a dispersion.
  • a dispersing agent e.g. Polyvinylpyrrolidone
  • a mixture according to the invention 15 parts by weight of a mixture according to the invention 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 in water results in an emulsion.
  • the formulation has an active ingredient content of 15% by weight.
  • 25 parts by weight of a mixture according to the invention are in 35 parts by weight of XyIoI with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • This mixture is added by means of an emulsifying machine (eg Ultraturrax) in 30 parts by weight of water and brought to a homogeneous emulsion. Dilution in water results in an emulsion.
  • the formulation has an active ingredient content of 25% by weight.
  • a mixture according to the invention 20 parts by weight of a mixture according to the invention are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient.
  • the active ingredient content in the formulation is 20% by weight.
  • Water-dispersible and Water-soluble Granules 50 parts by weight of a mixture according to the invention are finely ground with the addition of 50 parts by weight dispersing and wetting agents and by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules produced. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the formulation has an active ingredient content of 50% by weight.
  • 75 parts by weight of a mixture according to the invention are ground with the addition of 25 parts by weight of dispersants and wetting agents and silica gel in a rotor-Strator mill. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the active ingredient content of the formulation is 75% by weight.
  • 0.5 parts by weight of a mixture according to the invention are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with an active ingredient content of 0.5 wt .-%.
  • 10 parts by weight of a mixture according to the invention are in 90 parts by weight of a organic solvents, eg xylene, dissolved. This gives a product for direct application with an active ingredient content of 10 wt .-%.
  • a organic solvents eg xylene
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, misting, dusting, scattering or pouring.
  • the forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active substances.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.
  • 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 ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume
  • wetting agents To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, other pesticides, bactericides, if desired, also just immediately before use (tank mix), can be added. These agents are usually admixed to the mixtures according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.
  • adjuvants in this sense are in particular: organically modified polysiloxanes, eg Break Thru S 240 ® ; Alcohol alkoxylates, eg. As Atplus 245 ®, Atplus MBA 1303 ®, Plurafac LF 300 ® and Lutensol ON 30 ®; EO-PO block polymers, eg. B. Pluro- nic RPE 2035 ® and Genapol B ®; Alcohol ethoxylates, eg. As Lutensol XP 80 ®; and sodium dioctylsulfosuccinate, e. B. Leophen RA ®.
  • organically modified polysiloxanes eg Break Thru S 240 ®
  • Alcohol alkoxylates eg. As Atplus 245 ®, Atplus MBA 1303 ®, Plurafac LF 300 ® and Lutensol ON 30 ®
  • EO-PO block polymers eg. B. Pluro
  • the compounds I and II, or the mixtures or the corresponding formulations are applied by the harmful fungi, their habitat or the treated plants, seeds, soils, areas, materials or spaces with a fungicidally effective amount of the mixture, or the compounds I and II with separate application treated.
  • the application can be made before or after the attack by the harmful fungi.
  • the active compounds were prepared separately or together as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or dimethyl sulfoxide and the emulsifier Uniperol ® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent- Emulsifier from 99 to 1 ad 10 ml was filled. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.
  • Uniperol ® EL wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols
  • the active ingredients epoxiconazole and pyraclostrobin were used as a commercially available ready-made formulation and diluted with water to the stated active substance concentrations. The visually determined values for the percentage of affected leaf areas were converted into efficiencies as% of the untreated control.
  • the efficiency (W) was determined according to the formula of Abbot as follows:
  • ⁇ corresponds to the fungal infestation of the treated plants in% and ⁇ corresponds to the fungal infestation of the untreated (control) plants in%
  • the infestation of the treated plants corresponds to that of the untreated control plants; at an efficiency of 100, the treated plants had no infestation.
  • Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the drug concentration below. The following day, the leaves were infected with an aqueous spore suspension of Alternaria solani in 2% biomalt solution with a density of 0.17 ⁇ 10 6 spores / ml. The plants were then placed in a water vapor-saturated chamber at temperatures between 20 and 22 0 C. After 5 days, the disease on the untreated, but infected control plants had developed so strongly that the infestation could be determined visually in%.
  • Paprika seedlings of the cultivar "Neusiedler Ideal Elite” were sprayed to drip point with an aqueous suspension in the concentration of active compound stated below, after 2-3 leaves had developed well.
  • the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 10 6 spores / ml in a 2% aqueous biomalt solution.
  • the test plants were placed in a climatic chamber with 22 to 24 0 C, darkness and high humidity. After 5 days, the extent of fungal attack on the leaves could be determined visually in%.
  • Leaves of potted wheat seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below.
  • the suspension or emulsion was prepared as described above. 24 hours after the spray coating has dried on spores of wheat powdery mildew (Erysiphe [syn. graminis fomna specialis. tritici) pollinated.
  • the test plants were then placed in a greenhouse at temperatures between 20 and 24 ° C and 60 to 90% relative humidity. After 7 days, the extent of mildew development was determined visually in% infestation of the entire leaf area.

Abstract

The invention relates to fungicide mixtures containing in the form of active componenets: 1) at least one type of 3,5-disubstituted pyrazol-carboxylic acid biphenylamide of (formula I), wherein X=oxygen or sulfur, R1 and R2 = cyano, nitro, halogen, C1-C6-alkyl, C1-C6-halogenalkyl, methoxy, difluormethoxy or trifluormethoxy; R3 = halogen, C1-C4-alkyl or C1-C4-halogenalkyl; R4 = hydrogen or halogen; and (2) at least one type of active substance II selected from A) to F) groups: A) azole; B) strobilurin; C) carboxylic acid amides; D) heterocyclic compounds; E) carbamates and F) other fungicides in synergistically active quantity. A method for combating parasitic fungi by means of mixtures consisting of at least one type of compound I and at least one type of active substance II, the use of the compound(s) I with the active substances II for producing said mixtures and substances and seeds containing them are also disclosed.

Description

Fungizide Mischungen auf der Basis von 3,5-disubstituierten Pyrazolcarbonsäure- biphenylamidenFungicidal mixtures based on 3,5-disubstituted pyrazolecarboxylic acid biphenylamides
Beschreibungdescription
Die vorliegende Erfindung betrifft fungizide Mischungen, enthaltend als aktive Komponenten 1) mindestens ein 3,5-disubstituiertes Pyrazolcarbonsäurebiphenylamid der Formel IThe present invention relates to fungicidal mixtures comprising as active components 1) at least one 3,5-disubstituted pyrazolecarboxylic acid biphenylamide of the formula I.
Figure imgf000003_0001
in der die Substituenten folgende Bedeutungen haben:
Figure imgf000003_0001
in which the substituents have the following meanings:
X Sauerstoff oder Schwefel; R1 und R2 unabhängig voneinander Cyano, Nitro, Halogen, Ci-C6-Alkyl, CrC6-X oxygen or sulfur; R 1 and R 2 independently of one another are cyano, nitro, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -
Halogenalkyl, Methoxy, Difluormethoxy oder Trifluormethoxy; R3 Halogen, CrC4-AIkVl oder Ci-C4-Halogenalkyl; R4 Wasserstoff oder Halogen; undHaloalkyl, methoxy, difluoromethoxy or trifluoromethoxy; R 3 is halogen, -C 4 -alkyl or Ci-C 4 haloalkyl; R 4 is hydrogen or halogen; and
2) mindestens einen Wirkstoff Il ausgewählt aus den Gruppen A) bis F):2) at least one active ingredient II selected from the groups A) to F):
A) Azole ausgewählt aus Bitertanol, Bromuconazol, Cyproconazol, Difenocona- zol, Diniconazol, Enilconazol, Epoxiconazol, Fluquinconazol, Fenbuconazol, Flusilazol, Flutriafol, Hexaconazol, Imibenconazol, Ipconazol, Metconazol, Myclobutanil, Penconazol, Propiconazol, Prothioconazol, Simeconazol, Tria- dimefon, Triadimenol, Tebuconazol, Tetraconazol, Triticonazol, Prochloraz, Pefurazoat, Imazalil, Triflumizol, Cyazofamid, Benomyl, Carbendazim, Thia- bendazol, Fuberidazol, Ethaboxam, Etridiazol und Hymexazol,A) Azoles selected from bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, triadimefon , Triadimol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamide, benomyl, carbendazim, thiadanazole, fuberidazole, ethaboxam, etridiazole and hymexazole,
B) Strobilurine ausgewählt aus Azoxystrobin, Dimoxystrobin, Enestroburin, Fluo- xastrobin, Kresoxim-methyl, Methominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Trifloxystrobin, Enestroburin, (2-Chlor-5-[1-(3-methyl-benzyl- oxyimino)-ethyl]-benzyl)-carbaminsäure-methylester, (2-Chlor-5-[1-(6-methyl- pyridin-2-ylmethoxyimino)-ethyl]-benzyl)-carbaminsäure-methylester und 2-(ortho-(2,5-Dimethylphenyl-oxymethylen)phenyl)-3-methoxy-acrylsäure- methylester;B) Strobilurins selected from azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, methominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburin, (2-chloro-5- [1- (3-methylbenzyl-oxyimino) ethyl] -benzyl) -carbamic acid methyl ester, (2-chloro-5- [1- (6-methyl-pyridin-2-ylmethoxyimino) -ethyl] -benzyl) -carbamic acid methyl ester and 2- (ortho- (2 , 5-dimethylphenyl-oxymethylene) phenyl) -3-methoxy-acrylic acid methyl ester;
C) Carbonsäureamide ausgewählt aus Carboxin, Benalaxyl, Boscalid, Fenhex- amid, Flutolanil, Furametpyr, Mepronil, Metalaxyl, Mefenoxam, Ofurace, Oxa- dixyl, Oxycarboxin, Penthiopyrad, Thifluzamid, Tiadinil, 3,4-Dichlor-N-(2- cyanophenyO-isothiazol-δ-carbonsäureamid, Dimethomorph, Flumorph, FIu- metover, Fluopicolid (Picobenzamid), Zoxamid, Carpropamid, Diclocymet, Mandipropamid, N-(2-(4-[3-(4-Chlor-phenyl)-prop-2-ynyloxy]-3-methoxy- phenyl)-ethyl)-2-methansulfonylamino-3-nnethyl-butyrannid, N-(2-(4-[3-(4- Chlor-phenyl)-prop-2-ynyloxy]-3-methoxy-phenyl)-ethyl)-2-ethansulfonyl- amino-3-methyl-butyrannid, 3-(4-Chlor-phenyl)-3-(2-isopropoxy-carbonylamino- 3-methyl-butyrylamino)-propionsäure-nnethylester, Verbindungen der FormelC) Carboxylic acid amides selected from carboxin, benalaxyl, boscalid, fenhexamid, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, 3,4-dichloro-N- (2) cyanopheny O-isothiazole-δ-carboxamide, dimethomorph, flumorph, fl uidover, fluopicolide (picobenzamide), zoxamide, carpropamide, diclocymet, mandipropamide, N- (2- [4- [3- (4-chloro-phenyl) -propyl] 2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino-3-methylbutyrannide, N- (2- [4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] 3-methoxy-phenyl) -ethyl) -2-ethanesulfonyl-amino-3-methyl-butyrannide, 3- (4-chloro-phenyl) -3- (2-isopropoxycarbonylamino-3-methyl-butyrylamino) -propionic acid -Nnethyl ester, compounds of the formula
Figure imgf000004_0001
in der R5 Methyl oder Ethyl bedeutet,
Figure imgf000004_0001
in which R 5 is methyl or ethyl,
4-Difluormethyl-2-methyl-thiazol-5-carbonsäure-N-(4'-brom-biphenyl-2-yl)- amid, 4-Difluormethyl-2-methyl-thiazol-5-carbonsäure-N-(4'-trifluormethyl- biphenyl-2-yl)-amid, 4-Difluormethyl-2-methyl-thiazol-5-carbonsäure-N-(4'- chlor-3'-fluor-biphenyl-2-yl)-amid, 3-Difluormethyl-1-methyl-pyrazol-4- carbonsäure-N-(3',4'-dichlor-4-fluor-biphenyl-2-yl)-amid und 3,4-Dichlor- isothiazol-5-carbonsäure-N-(2-cyano-phenyl)-amid;4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4'-bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4 ' -trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4'-chloro-3'-fluorobiphenyl-2-yl) -amide, 3 Difluoromethyl-1-methyl-pyrazole-4-carboxylic acid N- (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide and 3,4-dichloro-isothiazole-5-carboxylic acid-N- (2-cyano-phenyl) -amide;
Heterocyclische Verbindungen ausgewählt aus Fluazinam, Pyrifenox, Bupirimate, Cyprodinil, Fenarimol, Ferimzon, Mepanipyrim, Nuarimol, Pyri- methanil, Triforin, Fenpiclonil, Fludioxonil, Aldimorph, Dodemorph, Fenpropi- morph, Tridemorph, Fenpropidin, Iprodion, Procymidon, Vinclozolin, Fam- oxadon, Fenamidon, Octhilinon, Probenazol, 5-Chlor-7-(4-methyl-piperidin-1- yl)-6-(2,4,6-trifluor-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin, Anilazin, Diclomezin, Pyroquilon, Proquinazid, Tricyclazol, die Verbindung der Formel IV (2-Butoxy- 6-iodo-3-proHeterocyclic compounds selected from fluazinam, pyrifenox, bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil, triforin, fenpiclonil, fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone, vinclozolin, family oxadone, fenamidone, octhilinone, probenazole, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1 , 5-a] pyrimidine, anilazine, diclomethine, pyroquilone, proquinazide, tricyclazole, the compound of formula IV (2-butoxy-6-iodo-3-pro
Figure imgf000004_0002
Figure imgf000004_0002
Acibenzolar-S-methyl, Captafol, Captan, Dazomet, Folpet, Fenoxanil, Quin- oxyfen und 3-(3-Brom-6-fluor-2-methyl-indol-1-sulfonyl)-[1 ,2,4]triazol-1-sulfon- säure-dimethylamid der Formel VAcibenzolar-S-methyl, captafol, captan, dazomet, folpet, fenoxanil, quinoxyfen and 3- (3-bromo-6-fluoro-2-methyl-indole-1-sulfonyl) - [1, 2,4] triazole -1-sulfonic acid dimethylamide of the formula V
(V);(V);
Figure imgf000004_0003
E) Carbamate ausgewählt aus Mancozeb, Maneb, Metam, Metiram, Ferbam, Propineb, Thiram, Zineb, Ziram, Diethofencarb, Iprovalicarb, Flubenthiavali- carb, Propamocarb, N-(1 -(1 -(4-cyanophenyl)ethansulfonyl)-but-2-yl)-carb- aminsäure-(4-fluorphenyl)ester, 3-(4-Chlor-phenyl)-3-(2-isopropoxycarbonyl- amino-3-meth l VI
Figure imgf000004_0003
E) Carbamates selected from Mancozeb, Maneb, Metam, Metiram, Ferbam, Propineb, Thiram, Zineb, Ziram, Diethofencarb, Iprovalicarb, Flubenthiavali- carb, Propamocarb, N- (1- (1 - (4-cyanophenyl) ethanesulfonyl) -but -2-yl) -carbamic acid (4-fluorophenyl) ester, 3- (4-chloro-phenyl) -3- (2-isopropoxycarbonyl-amino-3-methyl-VI
Figure imgf000005_0001
und Carbamatoximether der Formel VII
Figure imgf000005_0001
and carbamato oxime ethers of formula VII
Figure imgf000005_0002
in der Z für N oder CH steht;
Figure imgf000005_0002
Z is N or CH;
F) Sonstige Fungizide, ausgewählt aus Guanidine: Dodin, Iminoctadin, Guazatin, Antibiotika: Kasugamycin, Streptomycin, Polyoxin, Validamycin A, Nitrophenylderivate: Binapacryl, Dinocap, Dinobuton,F) Other fungicides selected from guanidines: dodin, iminoctadine, guazatine, antibiotics: kasugamycin, streptomycin, polyoxin, validamycin A, nitrophenyl derivatives: binapacryl, dinocap, dinobuton,
Schwefelhaltige Heterocyclylverbindungen: Dithianon, Isoprothiolan, Organometallverbindungen: Fentin-Salze wie Fentin-acetat, Organophosphorverbindungen: Edifenphos, Iprobenfos, Fosetyl, Fosetyl-Aluminium, Phosphorige Säure und deren Salze, Pyrazophos, ToIcIo- fos-methyl,Sulfur-containing heterocyclyl compounds: dithianone, isoprothiolane, organometallic compounds: fentin salts, such as fentin acetate, organophosphorus compounds: edifenphos, Iprobenfos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, toiolo-fos-methyl,
Organochlorverbindungen: Chlorthalonil, Dichlofluanid, Flusulfamid, Hexa- chlorbenzol, Phthalid, Pencycuron, Quintozen, Thiophanat-Methyl, ToIyI- fluanid,Organochlorine Compounds: Chlorothalonil, Dichlofluanid, Flusulfamide, Hexachlorobenzene, Phthalide, Pencycuron, Quintozen, Thiophanate-Methyl, Toiylfluanide,
Anorganische Wirkstoffe: Bordeaux Brühe, Kupferacetat, Kupferhydroxid, Kupferoxychlorid, basisches Kupfersulfat, Schwefel,Inorganic active ingredients: Bordeaux broth, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur,
Sonstige: Cyflufenamid, Cymoxanil, Dimethirimol, Ethirimol, Furalaxyl, Metrafenon und Spiroxamin;Other: Cyflufenamid, Cymoxanil, Dimethirimol, Ethirimol, Furalaxyl, Metrafenone and Spiroxamine;
in einer synergistisch wirksamen Menge.in a synergistically effective amount.
Außerdem betrifft die Erfindung ein Verfahren zur Bekämpfung von Schadpilzen mit der Mischung aus mindestens einer Verbindung I und mindestens einem der Wirkstoffe II, die Verwendung der Verbindungen I und Il zur Herstellung derartiger Mischungen sowie Mittel und Saatgut enthaltend diese Mischungen. Substituierte Biphenylamide der Formel I sind aus der EP-A 589 301 bekannt, in der auch ein Verfahren zu deren Herstellung sowie eine Liste möglicher Mischungspartner aus der Reihe der Fungizide, Bakterizide, Akarizide, Nematizide oder Insektizide angegeben ist.In addition, the invention relates to a method for controlling harmful fungi with the mixture of at least one compound I and at least one of the active compounds II, the use of the compounds I and II for the preparation of such mixtures and agents and seeds containing these mixtures. Substituted biphenylamides of the formula I are known from EP-A 589 301, in which a process for their preparation and a list of possible mixing partners from the series of fungicides, bactericides, acaricides, nematicides or insecticides is given.
Aus der WO 01/42223 sind ebenfalls substituierte Biphenylamide bekannt, die am Biphenylrest jedoch lediglich monosubstituiert sind.WO 01/42223 likewise discloses substituted biphenylamides which, however, are only monosubstituted on the biphenyl radical.
Aus der JP 09/132567 sind disubstituierte Biphenylanilide bekannt, die am Phenylring durch Trifluormethyl substituiert sind.From JP 09/132567 disubstituted biphenylanilides are known which are substituted on the phenyl ring by trifluoromethyl.
Aus der WO 2005/34628 sind Mischungen aus u. a. Pyrazolcarbonsäureamiden und verschiedenen anderen fungiziden Wirkstoffen bekannt. Die dortigen Pyrazolcarbon- säureamide unterscheiden sich von den vorliegenden Verbindungen I insbesondere durch das Substitutionsmuster am Biphenylrest.From WO 2005/34628 mixtures of u. a. Pyrazolcarbonsäureamiden and various other fungicidal agents known. The there pyrazolcarbonic acid amides differ from the present compounds I in particular by the substitution pattern on the biphenyl radical.
Aus der WO 2005/123689 und der WO 2005/123690 sind 2,4-disubstituierte Biphenylamide bekannt und aus der älteren deutschen Anmeldung Nr. 102005007160.0 sind 3,5-disubstituierte Biphenylamide bekannt.2,4-Disubstituted biphenylamides are known from WO 2005/123689 and WO 2005/123690, and 3,5-disubstituted biphenylamides are known from the earlier German Application No. 102005007160.0.
Die beschriebenen Biphenylamide und die bekannten Mischungen können jedoch, insbesondere bei niedrigen Aufwandmengen, nicht in vollem Umfang zufrieden stellen.However, the described biphenylamides and the known mixtures can not be completely satisfied, in particular at low application rates.
Die voranstehend als Komponente 2) genannten Wirkstoffe II, ihre Herstellung und ihre Wirkung gegen Schadpilze sind allgemein bekannt (vgl. z.B. http://www.hclrss.demon.co.uk/index.html); sie sind kommerziell erhältlich.The active compounds II mentioned above as component 2), their preparation and their action against harmful fungi are generally known (cf., for example, http://www.hclrss.demon.co.uk/index.html); they are commercially available.
Benalaxyl, Methyl N-(phenylacetyl)-N-(2,6-xylyl)-DL-alaninat (DE 29 03 612);Benalaxyl, methyl N- (phenylacetyl) -N- (2,6-xylyl) -DL-alaninate (DE 29 03 612);
Metalaxyl, Methyl N-(methoxyacetyl)-N-(2,6-xylyl)-DL-alaninat (GB 15 00 581); Ofurace, (RS)-α-(2-Chlor-N-2,6-xylylacetamido)-γ-butyrolacton [CAS RN 58810-48-3];Metalaxyl, methyl N- (methoxyacetyl) -N- (2,6-xylyl) -DL-alaninate (GB 15 00 581); Ofurace, (RS) -α- (2-chloro-N-2,6-xylylacetamido) -γ-butyrolactone [CAS RN 58810-48-3];
Oxadixyl, N-(2,6-dimethylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)acetamid (GBOxadixyl, N- (2,6-dimethylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide (GB
20 58 059);20 58 059);
Aldimorph, "4-Alkyl-2,5(oder 2,6)-dimethylmorpholin", enthaltend 65-75% 2,6-Dimethyl- morpholin und 25-35% 2,5-Dimethylmorpholin, enthaltend mehr als 85% 4-Dodecyl- 2,5(oder 2,6)-Dimethylmorpholin, wobei "alkyl" auch Octyl, Decyl, Tetradecyl undAldimorph, "4-alkyl-2,5 (or 2,6) -dimethylmorpholine" containing 65-75% 2,6-dimethylmorpholine and 25-35% 2,5-dimethylmorpholine containing more than 85% 4- Dodecyl-2,5 (or 2,6) -dimethylmorpholine, wherein "alkyl" also octyl, decyl, tetradecyl and
Hexadecyl mit einem cis/trans Verhältnis von 1 :1 einschließt [CAS RN 91315-15-0];Hexadecyl having a cis / trans ratio of 1: 1 [CAS RN 91315-15-0];
Dodin, 1-Dodecylguanidinium acetate (Plant Dis. Rep. 41 , S.1029 (1957));Dodin, 1-dodecylguanidinium acetate (Plant Dis. Rep. 41, p.1029 (1957));
Dodemorph, 4-Cyclododecyl-2,6-dimethylmorpholin (DE-A 1198125);Dodemorph, 4-cyclododecyl-2,6-dimethylmorpholine (DE-A 1198125);
Fenpropimorph, (RS)-cis-4-[3-(4-tert-Butylphenyl)-2-methylpropyl]-2,6-dimethyl- morpholin (DE-A 27 52 096);Fenpropimorph, (RS) -cis-4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine (DE-A 27 52 096);
Fenpropidin, (RS)-I -[3-(4-tert-Butylphenyl)-2-methylpropyl]piperidin (DE-A 27 52 096); Guazatin, Mischung der Reaktionsprodukte, erhalten aus der Amidierung von technischem lminodi(octamethylen)diamin, enthaltend verschiedene Guanidine und PoIy- amine [CAS RN 108173-90-6];Fenpropidin, (RS) -I - [3- (4-tert-butylphenyl) -2-methylpropyl] piperidine (DE-A 27 52 096); Guazatine, mixture of the reaction products obtained from the amidation of technical lminodi (octamethylene) diamine containing various guanidines and polyamines [CAS RN 108173-90-6];
Iminoctadin, 1 ,1'-lminodi(octamethylen)diguanidin (Congr. Plant Pathol., 1., S. 27 (1968);Iminoctadin, 1, 1'-lminodi (octamethylene) diguanidine (Congr. Plant Pathol., 1, 27 (1968);
Spiroxamin, (8-Tert-butyl-1 ,4-dioxaspiro[4.5]dec-2-yl)diethylamin (EP-A 281 842);Spiroxamine, (8-tert-butyl-1,4-dioxaspiro [4.5] dec-2-yl) diethylamine (EP-A 281 842);
Tridemorph, 2,6-Dimethyl-4-tridecylmorpholin (DE-A 11 64 152);Tridemorph, 2,6-dimethyl-4-tridecylmorpholine (DE-A 11 64 152);
Pyrimethanil, 4,6-Dimethylpyrimidin-2-yl-phenylannin (DD-A 151 404);Pyrimethanil, 4,6-dimethylpyrimidin-2-yl-phenyl-amine (DD-A 151 404);
Mepanipyrim, (4-Methyl-6-prop-1-inyl-pyrimidin-2-yl)-phenylamin (EP-A 224 339); Cyprodinil, (4-Cyclopropyl-6-methylpyrimidin-2-yl)phenylamin (EP-A 310 550);Mepanipyrim, (4-methyl-6-prop-1-ynyl-pyrimidin-2-yl) -phenylamine (EP-A 224 339); Cyprodinil, (4-cyclopropyl-6-methylpyrimidin-2-yl) -phenylamine (EP-A 310550);
Cycloheximid, 4-{(2R)-2-[(1S,3S,5S)-3,5-Dimethyl-2-oxocyclohexyl]-2-hydroxyethyl}pi- peridin-2,6-dion [CAS RN 66-81-9];Cycloheximide, 4 - {(2R) -2 - [(1S, 3S, 5S) -3,5-dimethyl-2-oxocyclohexyl] -2-hydroxyethyl} piperidine-2,6-dione [CAS RN 66-81 -9];
Griseofulvin, 7-Chlor-2',4,6-trimethoxy-6'-methylspiro[benzofuran-2(3H), 1 '-cyclohex-2'- ene]-3,4'-dion [CAS RN 126-07-8]; Kasugamycin, 3-O-[2-Amino-4-[(carboxyiminomethyl)amino]-2,3,4,6-tetradeoxy-α-D- arabino-hexopyranosyl]-D-chiro-inositol [CAS RN 6980-18-3];Griseofulvin, 7-chloro-2 ', 4,6-trimethoxy-6'-methylspiro [benzofuran-2 (3H), 1'-cyclohex-2'-ene] -3,4'-dione [CAS RN 126-07 -8th]; Kasugamycin, 3-O- [2-Amino-4 - [(carboxymiminomethyl) amino] -2,3,4,6-tetradeoxy-α-D-arabino-hexopyranosyl] -D-chiro-inositol [CAS RN 6980-18 -3];
Natamycin, (8E, 14E, 16E, 18E,20E)-(1 R,3S,5R,7R, 12R,22R,24S,25R,26S)-22-(3-Anni- no-3,6-dideoxy-ß-D-mannopyranosyloxy)-1 ,3,26-trihydroxy-12-methyl-10-oxo-6, 11 ,28- trioxatricyclo[22.3.1.05φctacosa-8,14,16,18,20-pentaene-25-carbonsäure [CAS RN 7681-93-8];Natamycin, (8E, 14E, 16E, 18E, 20E) - (1R, 3S, 5R, 7R, 12R, 22R, 24S, 25R, 26S) -22- (3-amino-3,6-dideoxy- β-D-mannopyranosyloxy) -1,3,26-trihydroxy-12-methyl-10-oxo-6,11,28-trioxatricyclo [22.3.1.0 5 φctacosa-8,14,16,18,20-pentaene-25 carboxylic acid [CAS RN 7681-93-8];
Polyoxin, 5-(2-Amino-5-O-carbamoyl-2-deoxy-L-xylonamido)-1 -(5-carboxy-1 ,2,3,4- tetrahydro-2,4-dioxopyrimidin-1-yl)-1 ,5-dideoxy-ß-D-allofuranuronsäure [CAS RNPolyoxine, 5- (2-Amino-5-O-carbamoyl-2-deoxy-L-xylonamido) -1- (5-carboxy-1,2,3,4-tetrahydro-2,4-dioxopyrimidin-1-yl ) -1, 5-dideoxy-.beta.-D-allofuranuronic acid [CAS RN
22976-86-9];22976-86-9];
Streptomycin, 1 ,1'-{1-L-(1,3,5/2,4,6)-4-[5-Deoxy-2-O-(2-deoxy-2-methylannino-α-L- glucopyranosyl)-3-C-formyl-α-L-lyxofuranosyloxy]-2,5,6-trihydroxycyclohex-1 ,3- ylene}diguanidin (J. Am. Chem. Soc. 69, S.1234 (1947));Streptomycin, 1,1 '- {1-L- (1,3,5 / 2,4,6) -4- [5-deoxy-2-O- (2-deoxy-2-methylannino-α-L-) glucopyranosyl) -3-C-formyl-α-L-xyxofuranosyloxy] -2,5,6-trihydroxycyclohex-1, 3-ylene} diguanidine (J. Am. Chem. Soc. 69, p.1234 (1947));
Bitertanol, ß-([1 , 1 '-Biphenyl]-4-yloxy)-α-(1 , 1 -dimethylethyl)-1 H-1 ,2,4-triazol-1 -ethanolBitertanol, β - ([1,1'-biphenyl] -4-yloxy) -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol
(DE 23 24 020);(DE 23 24 020);
Bromuconazol, 1 -[[4-Brom-2-(2,4-dichlorphenyl)tetrahydro-2-furanyl]methyl]-1 H-1 ,2,4- triazol (Proc. 1990 Br. Crop. Prot. Conf. - Pests Dis., Bd. 1, S. 459);Bromuconazole, 1 - [[4-bromo-2- (2,4-dichlorophenyl) tetrahydro-2-furanyl] methyl] -1H-1, 2,4-triazole (Proc. 1990 Br. Crop. Prot. Conf. - Pests Dis., Vol. 1, p. 459);
Cyproconazol, 2-(4-Chlorphenyl)-3-cyclopropyl-1 -[1 ,2,4]triazol-1 -ylbutan-2-olCyproconazole, 2- (4-chlorophenyl) -3-cyclopropyl-1 - [1, 2,4] triazole-1-yl-butan-2-ol
(US 4,664,696);(US 4,664,696);
Difenoconazol, 1 -{2-[2-Chlor-4-(4-chlorphenoxy)phenyl]-4-methyl-[1 ,3]dioxolan-2- ylmethyl}-1 H-[1 ,2,4]triazol (GB-A 2 098 607); Diniconazol, (ßE)-ß-[(2,4-Dichlorphenyl)methylen]-α-(1 , 1 -dimethylethyl)-1 H-1 ,2,4- triazol-1 -ethanol (Noyaku Kagaku, 1983, Bd. 8, S. 575);Difenoconazole, 1 - {2- [2-chloro-4- (4-chlorophenoxy) phenyl] -4-methyl- [1,3-dioxolan-2-ylmethyl} -1 H- [1,2,4] triazole ( GB-A 2 098 607); Diniconazole, (βE) -β - [(2,4-dichlorophenyl) methylene] -α- (1, 1-dimethylethyl) -1H-1, 2,4-triazole-1-ethanol (Noyaku Kagaku, 1983, Vol 8, p. 575);
Enilconazol (Imazalil), 1-[2-(2,4-Dichlorphenyl)-2-(2-propenyloxy)ethyl]-1 H-imidazolEnilconazole (imazalil), 1- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -1H-imidazole
(Fruits 28, S. 545, 1973);(Fruits 28, p. 545, 1973);
Epoxiconazol, (2RS,3SR)-1 -[3-(2-Chlorphenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl]-1 H- 1 ,2,4-triazol (EP-A 196 038);Epoxiconazole, (2RS, 3SR) -1 - [3- (2-chlorophenyl) -2,3-epoxy-2- (4-fluorophenyl) propyl] -1H-1,2,4-triazole (EP-A 196 038);
Fenbuconazol, α-[2-(4-Chlorphenyl)ethyl]-α-phenyl-1 H-1 ,2,4-triazole-1-propannitrilFenbuconazole, α- [2- (4-chlorophenyl) ethyl] -α-phenyl-1H-1, 2,4-triazole-1-propanenitrile
(Proc. 1988 Br. Crop Prot. Conf. - Pests Dis., Bd. 1 , S. 33); Fluquinconazol, 3-(2,4-Dichlorphenyl)-6-fluor-2-[1 ,2,4]-triazol-1 -yl-3H-quinazolin-4-on(Proc., 1988 Br. Crop Prot. Conf. - Pests Dis., Vol. 1, p. 33); Fluquinconazole, 3- (2,4-dichlorophenyl) -6-fluoro-2- [1,2,4] triazole-1-yl-3H-quinazolin-4-one
(Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 411 (1992));(Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 411 (1992));
Flusilazol, 1-{[Bis-(4-fluorophenyl)methylsilanyl]methyl}-1 H-[1 ,2,4]triazol (Proc. Br. CropFlusilazole, 1 - {[bis (4-fluorophenyl) methylsilanyl] methyl} -1 H- [1,2,4] triazole (Proc. Br. Crop
Prot. Conf.-Pests Dis., Bd. 1, S. 413 (1984)); Flutriafol, α-(2-Fluorphenyl)-α-(4-fluorphenyl)-1 H-1 ,2,4-triazol-1 -ethanol (EP-A 15 756);Prot. Conf.-Pests Dis., Vol. 1, p. 413 (1984)); Flutriafol, α- (2-fluorophenyl) -α- (4-fluorophenyl) -1H-1, 2,4-triazole-1-ethanol (EP-A 15,756);
Hexaconazol, 2-(2,4-Dichlorphenyl)-1-[1 ,2,4]triazol-1-yl-hexan-2-ol (CAS RNHexaconazole, 2- (2,4-dichlorophenyl) -1- [1,2,4] triazol-1-yl-hexan-2-ol (CAS RN
79983-71-4);79983-71-4);
Ipconazol, 2-[(4-Chlorphenyl)methyl]-5-(1-methylethyl)-1-(1 H-1 ,2,4-triazol-1-yl- methyl)cyclopentanol (EP-A 267 778); Metconazol, 5-(4-Chlorbenzyl)-2,2-dimethyl-1 -[1 ,2,4]triazol-1 -ylmethylcyclopentanolIpconazole, 2 - [(4-chlorophenyl) methyl] -5- (1-methylethyl) -1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (EP-A 267,778); Metconazole, 5- (4-chlorobenzyl) -2,2-dimethyl-1 - [1, 2,4] triazole-1-ylmethylcyclopentanol
(GB 857 383);(GB 857,383);
Myclobutanil, 2-(4-Chlorphenyl)-2-[1 ,2,4]triazol-1-ylmethyl-pentannitril (CAS RN 88671-Myclobutanil, 2- (4-chlorophenyl) -2- [1,2,4] triazol-1-ylmethylpentanenitrile (CAS RN 88671-
89-0);89-0);
Penconazol, 1-[2-(2,4-Dichlorphenyl)pentyl]-1 H-[1 ,2,4]triazol (Pesticide Manual, 12. Auflage 2000, S. 712);Penconazole, 1- [2- (2,4-dichlorophenyl) pentyl] -1 H- [1,2,4] triazole (Pesticide Manual, 12th Edition 2000, p. 712);
Propiconazol, 1 -[[2-(2,4-Dichlorphenyl)-4-propyl-1 ,3-dioxolan-2-yl]methyl]-1 H-1 ,2,4- triazol (BE 835 579);Propiconazole, 1 - [[2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl] methyl] -1H-1, 2,4-triazole (BE 835,579);
Prochloraz, lmidazol-1-carbonsäure-propyl-[2-(2,4,6-trichlorphenoxy)-ethyl]-amidProchlorazole, imidazole-1-carboxylic acid-propyl- [2- (2,4,6-trichlorophenoxy) -ethyl] -amide
(US 3,991 ,071); Prothioconazol, 2-[2-(1 -Chlorcyclopropyl)-3-(2-chlorphenyl)-2-hydroxypropyl]-2,4- dihydro-[1 ,2,4]triazol-3-thion (WO 96/16048);(US 3,991,071); Prothioconazole, 2- [2- (1-Chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro- [1,2,4] triazole-3-thione (WO 96/16048) ;
Simeconazol, α-(4-Fluorophenyl)-α-[(trimethylsilyl)methyl]-1 H-1 ,2,4-triazol-1 -ethanolSimeconazole, α- (4-fluorophenyl) -α - [(trimethylsilyl) methyl] -1H-1,2,4-triazole-1-ethanol
[CAS RN 149508-90-7];[CAS RN 149508-90-7];
Tebuconazol, 1 -(4-Chlorphenyl)-4,4-dimethyl-3-[1 ,2,4]triazol-1 -ylmethyl-pentan-3-ol (EP-A 40 345);Tebuconazole, 1- (4-chlorophenyl) -4,4-dimethyl-3- [1,2,4] triazole-1-ylmethylpentan-3-ol (EP-A 40 345);
Tetraconazol, 1 -[2-(2,4-Dichlorphenyl)-3-(1 , 1 ,2,2-tetrafluorethoxy)propyl]-1 H-1 ,2,4- triazol (EP-A 234 242);Tetraconazole, 1 - [2- (2,4-dichlorophenyl) -3- (1,1,2,2-tetrafluoroethoxy) propyl] -1H-1, 2,4-triazole (EP-A 234 242);
Triadimefon, 1 -(4-Chlorphenoxy)-3,3-dimethyl-1 -(1 H-1 ,2,4-triazol-1 -yl)-2-butanon (BETriadimefon, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1, 2,4-triazol-1-yl) -2-butanone (BE
793 867); Triadimenol, ß-(4-Chlorphenoxy)-α-(1 , 1 -dimethylethyl)-1 H-1 ,2,4-triazol-1 -ethanol (DE-A793 867); Triadimenol, β- (4-chlorophenoxy) -α- (1, 1-dimethylethyl) -1H-1, 2,4-triazole-1-ethanol (DE-A
23 24 010);23 24 010);
Triflumizol, (4-Chlor-2-trifluormethylphenyl)-(2-propoxy-1 -[1 ,2,4]triazol-1 -yl-ethyliden)- amin (JP-A 79/119 462);Triflumizole, (4-chloro-2-trifluoromethylphenyl) - (2-propoxy-1 - [1, 2,4] triazole-1-yl-ethylidene) -amine (JP-A 79/119 462);
Triticonazol, (5E)-5-[(4-Chlorphenyl)methylen]-2,2-dimethyl-1 -(1 H-1 ,2,4-triazol-1 - ylmethyl)cyclopentanol (FR 26 41 277);Triticonazole, (5E) -5 - [(4-chlorophenyl) methylene] -2,2-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (FR 26 41 277);
Iprodion, 3-(3,5-Dichlorphenyl)-2,4-dioxo-imidazolidin-1-carbonsäureisopropylamid (GBIprodione, 3- (3,5-dichlorophenyl) -2,4-dioxo-imidazolidine-1-carboxylic acid isopropylamide (GB
13 12 536);13 12 536);
Myclozolin, (RS)-3-(3,5-Dichlorphenyl)-5-methoxymethyl-5-methyl-1 ,3-oxazolidin-2,4- dion [CAS RN 54864-61-8]; Procymidon, N-(3,5-Dichlorphenyl)-1 ,2-dimethylcyclopropan-1 ,2-dicarboximid (USMyclozoline, (RS) -3- (3,5-dichlorophenyl) -5-methoxymethyl-5-methyl-1,3-oxazolidine-2,4-dione [CAS RN 54864-61-8]; Procymidone, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide (US Pat
3,903,090); Vinclozolin, 3-(3,5-Dichlorphenyl)-5-methyl-5-vinyl-oxazolidin-2,4-dion (DE-A3,903,090); Vinclozoline, 3- (3,5-dichlorophenyl) -5-methyl-5-vinyl-oxazolidine-2,4-dione (DE-A
22 07 576);22 07 576);
Ferbam, Eisen(3+)dimethyldithiocarbamat (US 1 ,972,961);Ferbam, iron (3+) dimethyldithiocarbamate (US 1,972,961);
Nabam, Dinatriumethylenbis(dithiocarbamat) (US 2,317,765); Maneb, Mangan-ethylenbis(dithiocarbamat) (US 2,504,404);Nabam, disodium ethylenebis (dithiocarbamate) (US 2,317,765); Maneb, manganese ethylene bis (dithiocarbamate) (US 2,504,404);
Mancozeb, Mangan-ethylenbis(dithiocarbamat)-polymerkomplex-Zinksalz (GBMancozeb, manganese ethylene bis (dithiocarbamate) polymer complex zinc salt (GB
996 264);996 264);
Metam, Methyldithiocarbaminsäure (US 2,791 ,605);Metam, methyldithiocarbamic acid (US 2,791,605);
Metiram, Zinkammoniat-ethylenbis(dithiocarbamat) (US 3,248,400); Propineb, Zink Propylenbis(dithiocarbamat) Polymer (BE 611 960);Metiram, zinc ammonium ethylenebis (dithiocarbamate) (US 3,248,400); Propineb, zinc propylene bis (dithiocarbamate) polymer (BE 611 960);
Polycarbamat, Bis(dimethylcarbamodithioato-κS,κS')[μ-[[1 ,2-ethandiylbis[carbamo- dithioato-κS,κS']](2-)]]di[zinc] [CAS RN 64440-88-6];Polycarbamate, bis (dimethylcarbamodithioato-κS, κS ') [μ - [[1,2-ethanediylbis [carbamoedithioato-κS, κS']] (2 -)]] di [zinc] [CAS RN 64440-88-6 ];
Thiram, Bis(dimethylthiocarbamoyl)disulfid (DE-A 642 532);Thiram, bis (dimethylthiocarbamoyl) disulfide (DE-A 642 532);
Ziram, Dimethyldithiocarbamat [CAS RN 137-30-4]; Zineb, Zink-ethylenbis(dithiocarbamat) (US 2,457,674);Ziram, dimethyldithiocarbamate [CAS RN 137-30-4]; Zineb, zinc ethylenebis (dithiocarbamate) (US 2,457,674);
Anilazin, 4,6-Dichlor-N-(2-chlorphenyl)-1 ,3,5-triazin-2-amin (US 2,720,480);Anilazine, 4,6-dichloro-N- (2-chlorophenyl) -1, 3,5-triazin-2-amine (US 2,720,480);
Benomyl, 2-Acetylaminobenzimidazol-1-carbonsäurebutylamid (US 3,631 ,176);Benomyl, 2-acetylaminobenzimidazole-1-carboxylic acid butylamide (US 3,631,176);
Boscalid, 2-Chlor-N-(4'-chlorbiphenyl-2-yl)nicotinamid (EP-A 545 099);Boscalid, 2-chloro-N- (4'-chlorobiphenyl-2-yl) nicotinamide (EP-A 545 099);
Carbendazim, (1 H-Benzimidazol-2-yl)-carbaminsäuremethylester (US 3,657,443); Carboxin, 5,6-Dihydro-2-methyl-N-phenyl-1 ,4-oxathiin-3-carboxamid (US 3,249,499);Carbendazim, (1 H-benzimidazol-2-yl) -carbamic acid methyl ester (US 3,657,443); Carboxin, 5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-carboxamide (US 3,249,499);
Oxycarboxin, 5,6-Dihydro-2-methyl-1 ,4-oxathiin-3-carboxanilid 4,4-dioxid (USOxycarboxine, 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide 4,4-dioxide (US
3,399,214);3,399,214);
Cyazofamid, 4-Chlor-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1 H-imidazol-1 -Sulfonamid (CAS RN 120116-88-3]; Dazomet, 3,5-Dimethyl-1 ,3,5-thiadiazinan-2-thion (Bull. Soc. Chim. Fr. Vol. 15, p. 891Cyazofamide, 4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazole-1-sulfonamide (CAS RN 120116-88-3]; dazomet, 3,5-dimethyl- 1, 3,5-thiadiazinan-2-thione (Bull. Soc. Chim. Fr. Vol. 15, p. 891
(1897));(1897));
Diflufenzopyr, 2-{1-[4-(3,5-Difluorphenyl)semicarbazono]ethyl}nicotinsäure [CAS RNDiflufenzopyr, 2- {1- [4- (3,5-difluorophenyl) semicarbazono] ethyl} nicotinic acid [CAS RN
109293-97-2];109293-97-2];
Dithianon, 5, 10-Dioxo-5, 10-dihydronaphtho[2,3-b][1 ,4]dithiin-2,3-dicarbonitril (GB 857 383);Dithianone, 5,10-dioxo-5,10-dihydronaphtho [2,3-b] [1,4] dithiine-2,3-dicarbonitrile (GB 857,383);
Famoxadon, (RS)-3-Anilino-5-methyl-5-(4-phenoxyphenyl)-1 ,3-oxazolidin-2,4-dionFamoxadone, (RS) -3-anilino-5-methyl-5- (4-phenoxyphenyl) -1,3-oxazolidine-2,4-dione
[CAS RN 131807-57-3];[CAS RN 131807-57-3];
Fenamidon, (S)-1-Anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-on [CAS RNFenamidone, (S) -1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one [CAS RN
161326-34-7]; Fenarimol, α-(2-Chlorphenyl)-α-(4-chlorphenyl)-5-pyrimidinmethanol (GB 12 18 623);161326-34-7]; Fenarimol, α- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidinemethanol (GB 12 18 623);
Fuberidazole, 2-(2-Furanyl)-1 H-benzimidazol (DE-A 12 09 799);Fuberidazole, 2- (2-furanyl) -1H-benzimidazole (DE-A 12 09 799);
Flutolanil, α,α,α-Trifluor-3'-isopropoxy-o-toluanilid (JP 1104514);Flutolanil, α, α, α-trifluoro-3'-isopropoxy-o-toluanilide (JP 1104514);
Furametpyr, 5-Chlor-N-(1 ,3-dihydro-1 , 1 ,3-trimethyl-4-isobenzofuranyl)-1 ,3-dimethyl-1 H- pyrazol-4-carboxamid [CAS RN 123572-88-3]; Isoprothiolan, Diisopropyl 1 ,3-dithiolan-2-ylidenmalonat (Proc. Insectic. Fungic. Conf. 8,Furametpyr, 5-chloro-N- (1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl) -1,3-dimethyl-1H-pyrazole-4-carboxamide [CAS RN 123572-88-3 ]; Isoprothiolane, diisopropyl 1, 3-dithiolan-2-ylidenmalonate (Proc. Insectic. Fungic. Conf.
Bd. 2, S. 715 (1975));Vol. 2, p. 715 (1975));
Mepronil, 3'-lsopropoxy-o-toluanilid (US 3,937,840); Nuarimol, α-(2-Chlorphenyl)-α-(4-fluorphenyl)-5-pyrimidinnnethanol (GB 12 18 623);Mepronil, 3'-isopropoxy-o-toluanilide (US 3,937,840); Nuarimol, α- (2-chlorophenyl) -α- (4-fluorophenyl) -5-pyrimidine-methanol (GB 12 18 623);
Fluopicolid (Picobenzamid), 2,6-Dichlor-N-(3-chlor-5-trifluormethyl-pyridin-2-ylmethyl)- benzamid (WO 99/42447);Fluopicolide (picobenzamide), 2,6-dichloro-N- (3-chloro-5-trifluoromethylpyridin-2-ylmethyl) benzamide (WO 99/42447);
Probenazol, 3-Allyloxy-1 ,2-benzothiazol 1 ,1-dioxid (Agric. Biol. Chem. 37, S. 737 (1973);Probenazole, 3-allyloxy-1,2-benzothiazole 1,1-dioxide (Agric., Biol. Chem. 37, p.737 (1973);
Proquinazid, 6-lod-2-propoxy-3-propylquinazolin-4(3H)-on (WO 97/48684);Proquinazide, 6-iodo-2-propoxy-3-propylquinazolin-4 (3H) -one (WO 97/48684);
Pyrifenox, 2',4'-Dichlor-2-(3-pyridyl)acetophenon (EZ)-O-methyloxim (EP 49 854);Pyrifenox, 2 ', 4'-dichloro-2- (3-pyridyl) acetophenone (EZ) -O-methyloxime (EP 49 854);
Pyroquilon, 1,2,5,6-Tetrahydropyrrolo[3,2,1-ij]quinolin-4-on (GB 139 43 373);Pyroquilone, 1,2,5,6-tetrahydropyrrolo [3,2,1-ij] quinolin-4-one (GB 139 43 373);
Quinoxyfen, 5,7-Dichlor-4-(4-fluorphenoxy)quinolin (US 5,240,940); Silthiofam, N-Allyl-4,5-dimethyl-2-(trinnethylsilyl)thiophen-3-carboxannid [CAS RNQuinoxyfen, 5,7-dichloro-4- (4-fluorophenoxy) quinoline (US 5,240,940); Silthiofam, N-allyl-4,5-dimethyl-2- (triethylsilyl) thiophene-3-carboxannide [CAS RN
175217-20-6];175217-20-6];
Thiabendazol, 2-(1 ,3-Thiazol-4-yl)benzimidazol (US 3,017,415);Thiabendazole, 2- (1,3-thiazol-4-yl) benzimidazole (US 3,017,415);
Thifluzamid, 2',6'-Dibrom-2-methyl-4'-trifluornnethoxy-4-trifluornnethyl-1 ,3-thiazol-5- carboxanilid [CAS RN 130000-40-7]; Thiophanat-methyl, 1 ,2-Phenylenbis(iminocarbonothioyl)bis(dimethylcarbannat) (DE-AThifluzamide, 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4-trifluoromethyl-1, 3-thiazole-5-carboxanilide [CAS RN 130000-40-7]; Thiophanate-methyl, 1, 2-phenylenebis (iminocarbonothioyl) bis (dimethylcarbannate) (DE-A
19 30 540);19 30 540);
Tiadinil, S'-Chlor^'-dimethyl-I ^S-thiadiazol-δ-carboxanilid [CAS RN 223580-51-6];Tiadinil, S'-chloro '' - dimethyl-1S-thiadiazole-6-carboxanilide [CAS RN 223580-51-6];
Tricyclazol, 5-Methyl-1 ,2,4-triazolo[3,4-b][1 ,3]benzothiazol [CAS RN 41814-78-2];Tricyclazole, 5-methyl-1,2,4-triazolo [3,4-b] [1,3] benzothiazole [CAS RN 41814-78-2];
Triforin, N,N'-{Piperazin-1 ,4-diylbis[(trichlormethyl)methylen]}diformamid (DE-A 19 01 421);Triforin, N, N '- {piperazine-1, 4-diylbis [(trichloromethyl) methylene] diformamide (DE-A 19 01 421);
5-Chlor-7-(4-methyl-piperidin-1 -yl)-6-(2,4,6-trifluor-phenyl)-[1 ,2,4]triazolo[1 ,5- a]pyrimidin (WO 98/46607);5-Chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine (WO 98/46607);
Bordeauxbrühe, Mischung aus CuSO4 x 3Cu(OH)2 x 3CaSO4 [CAS RN 8011-63-0];Bordeaux broth, mixture of CuSO 4 .3Cu (OH) 2 .3CaSO 4 [CAS RN 8011-63-0];
Kupferacetat, Cu(OCOCH3)2 [CAS RN 8011-63-0]; Kupferoxychlorid, Cu2CI(OH)3 [CAS RN 1332-40-7];Copper acetate, Cu (OCOCH 3 ) 2 [CAS RN 8011-63-0]; Copper oxychloride, Cu 2 Cl (OH) 3 [CAS RN 1332-40-7];
Basisches Kupfersulfat, CuSO4 [CAS RN 1344-73-6];Basic copper sulfate, CuSO 4 [CAS RN 1344-73-6];
Binapacryl, (RS)-2-sec-Butyl-4,6-dinitrophenyl 3-methylcrotonat [CAS RN 485-31-4];Binapacryl, (RS) -2-sec-butyl-4,6-dinitrophenyl 3-methylcrotonate [CAS RN 485-31-4];
Dinocap, Mischung aus 2,6-Dinitro-4-octylphenylcrotonat und 2,4-Dinitro-6-octyl- phenylcrotonat, wobei "octyl" eine Mischung aus 1-Methylheptyl, 1-Ethylhexyl und 1- Propylpentyl ist (US 2,526,660);Dinocap, a mixture of 2,6-dinitro-4-octylphenyl crotonate and 2,4-dinitro-6-octylphenyl crotonate, wherein "octyl" is a mixture of 1-methylheptyl, 1-ethylhexyl and 1-propylpentyl (US 2,526,660);
Dinobuton, (RS)-2-sec-Butyl-4,6-dinitrophenyl isopropyl carbonat [CAS RN 973-21-7];Dinobutone, (RS) -2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate [CAS RN 973-21-7];
Nitrothal-isopropyl, diisopropyl 5-nitroisophthalat (Proc. Br. Insectic. Fungic. Conf. 7.,Nitrothal isopropyl, diisopropyl 5-nitroisophthalate (Proc. Br. Insectic. Fungic. Conf.
Bd. 2, S. 673 (1973));Vol. 2, p. 673 (1973));
Fenpiclonil, 4-(2,3-Dichlorphenyl)-1 H-pyrrol-3-carbonitril (Proc. 1988 Br. Crop Prot. Conf. - Pests Dis., Bd. 1 , S. 65);Fenpiclonil, 4- (2,3-dichlorophenyl) -1H-pyrrole-3-carbonitrile (Proc. 1988 Br. Crop Prot. Conf. - Pests Dis., Vol. 1, p.
Fludioxonil, 4-(2,2-Difluorbenzo[1 ,3]dioxol-4-yl)-1 H-pyrrol-3-carbonitril (The PesticideFludioxonil, 4- (2,2-difluorobenzo [1,3] dioxol-4-yl) -1H-pyrrole-3-carbonitrile (The Pesticide
Manual, Hrsg.: The British Crop Protection Council, 10. Auflage 1995, S. 482);Manual, Ed .: The British Crop Protection Council, 10th Edition 1995, p. 482);
Acibenzolar-S-methyl, Methyl 1,2,3-benzothiadiazol-7-carbothioat [CAS RN 135158-Acibenzolar-S-methyl, methyl 1,2,3-benzothiadiazole-7-carbothioate [CAS RN 135158-
54-2]; Flubenthiavalicarb (Benthiavalicarb), {(S)-1 -[(1 R)-1 -(6-Fluorbenzothiazol-2-yl)- ethylcarbamoyl]-2-methylpropyl}-carbaminsäureisopropylester (JP-A 09/323 984); Carpropamid, 2,2-Dichlor-N-[1 -(4-chlorphenyl)ethyl]-1 -ethyl-3-methylcyclopropan- carboxamid [CAS RN 104030-54-8];54-2]; Flubenthiavalicarb (benthiavalicarb), {(S) -1 - [(1 R) -1 - (6-fluorobenzothiazol-2-yl) ethylcarbamoyl] -2-methylpropyl} -carbamic acid isopropyl ester (JP-A 09/323 984); Carpropamide, 2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methylcyclopropane carboxamide [CAS RN 104030-54-8];
Chlorthalonil, 2,4,5,6-Tetrachlorisophthalonitril (US 3,290,353);Chlorothalonil, 2,4,5,6-tetrachloroisophthalonitrile (US 3,290,353);
Cyflufenamid, (Z)-N-[α-(Cyclopropylmethoxyimino)-2,3-difluor-6-(trifluornnethyl)benzyl]- 2-phenylacetamid (WO 96/19442);Cyflufenamide, (Z) -N- [α- (cyclopropylmethoxyimino) -2,3-difluoro-6- (trifluoromethyl) benzyl] -2-phenylacetamide (WO 96/19442);
Cymoxanil, 1-(2-Cyano-2-methoxyiminoacetyl)-3-ethylhamstoff (US 3,957,847);Cymoxanil, 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea (US 3,957,847);
Diclomezin, 6-(3,5-Dichlorphenyl-p-tolyl)pyridazin-3(2H)-on (US 4,052,395);Diclomethine, 6- (3,5-dichlorophenyl-p-tolyl) pyridazine-3 (2H) -one (US 4,052,395);
Diclocymet, (RS)-2-Cyano-N-[(R)-1-(2,4-dichlorphenyl)ethyl]-3,3-dimethylbutyrannidDiclocymet, (RS) -2-cyano-N - [(R) -1- (2,4-dichlorophenyl) ethyl] -3,3-dimethylbutyrannide
[CAS RN 139920-32-4]; Diethofencarb, Isopropyl 3,4-diethoxycarbanilat (EP-A 78 663);[CAS RN 139920-32-4]; Diethofencarb, isopropyl 3,4-diethoxycarbanilate (EP-A 78 663);
Edifenphos, O-Ethyl S,S-diphenyl phosphorodithioat (DE-A 14 93 736);Edifenphos, O-ethyl S, S-diphenyl phosphorodithioate (DE-A 14 93 736);
Ethaboxam, N-(Cyano-2-thienylmethyl)-4-ethyl-2-(ethylamino)-5-thiazolcarboxannidEthaboxam, N- (cyano-2-thienylmethyl) -4-ethyl-2- (ethylamino) -5-thiazolecarboxannide
(EP-A 639 574);(EP-A 639 574);
Fenhexamid, N-(2,3-dichlor-4-hydroxyphenyl)-1 -methylcyclohexancarboxamid (Proc. Br. Crop Prot. Conf. - Pests Dis., 1998, Bd. 2, S. 327);Fenhexamid, N- (2,3-dichloro-4-hydroxyphenyl) -1-methylcyclohexanecarboxamide (Proc. Br. Crop Prot. Conf. - Pests Dis., 1998, Vol. 2, p. 327);
Fentin-acetat, Triphenylzinn (US 3,499,086);Fentin acetate, triphenyltin (US 3,499,086);
Fenoxanil, N-(1-Cyano-1 ,2-dimethylpropyl)-2-(2,4-dichlorphenoxy)propanamid (EP-AFenoxanil, N- (1-cyano-1,2-dimethylpropyl) -2- (2,4-dichlorophenoxy) propanamide (EP-A
262 393);262 393);
Ferimzone, (Z)-2'-Methylacetophenon-4,6-dimethylpyrimidin-2-ylhydrazon [CAS RN 89269-64-7];Ferric zone, (Z) -2'-methylacetophenone-4,6-dimethylpyrimidin-2-ylhydrazone [CAS RN 89269-64-7];
Fluazinam, S-Chlor-N-^-chlor^.β-dinitro^-^rifluormethyOphenylJ-S-^rifluormethyl)^- pyridinamin (The Pesticide Manual, Hrsg.: The British Crop Protection Council, 10.Fluazinam, S-chloro-N - ^ - chloro-β, -β-dinitro ^ -rifluoromethyl-phenyl-S-rifluoromethyl) -pyridinamine (The Pesticide Manual, Ed. The British Crop Protection Council, 10.
Auflage 1995, S. 474);Edition 1995, p. 474);
Fosetyl, Fosetyl-Aluminum, Ethylphosphonat (FR 22 54 276); Iprovalicarb, [(1S)-2-Methyl-1-(1-p-tolyl-ethylcarbamoyl)-propyl]carbaminsäure- isopropylester (EP-A 472 996);Fosetyl, Fosetyl Aluminum, Ethyl Phosphonate (FR 22 54 276); Iprovalicarb, [(1S) -2-methyl-1- (1-p-tolyl-ethylcarbamoyl) -propyl] -carbamic acid isopropyl ester (EP-A 472 996);
Hexachlorbenzol (C. R. Seances Acad. Agric. Fr., Vol. 31 , S. 24 (1945);Hexachlorobenzene (C.R. Seances Acad. Agric. Fr., Vol. 31, p. 24 (1945);
Mandipropamid, (RS)-2-(4-Chlorphenyl)-N-[3-methoxy-4-(prop-2-ynyloxy)phenethyl]-2-Mandipropamide, (RS) -2- (4-chlorophenyl) -N- [3-methoxy-4- (prop-2-ynyloxy) phenethyl] -2-
(prop-2-ynyloxy)acetamid (WO 03/042166); Metrafenon, 3'-Brom-2,3,4,6'-tetramethoxy-2',6-dimethylbenzophenon (US 5,945,567);(prop-2-ynyloxy) acetamide (WO 03/042166); Metrafenone, 3'-bromo-2,3,4,6'-tetramethoxy-2 ', 6-dimethylbenzophenone (US 5,945,567);
Pencycuron, i-^-Chlorbenzy^-i-cyclopentyl-S-phenylhamstoff (DE-A 27 32 257);Pencycuron, i - ^ - chlorobenzy ^ -i-cyclopentyl-S-phenylurea (DE-A 27 32 257);
Penthiopyrad, (RS)-N-[2-(1 ,3-Dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluormethyl)-1 H- pyrazol-4-carboxamid (JP 10/130268);Penthiopyrad, (RS) -N- [2- (1, 3-dimethylbutyl) -3-thienyl] -1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxamide (JP 10/130268);
Propamocarb, 3-(Dimethylamino)propylcarbaminsäureisopropylester (DE-A 1567 169); Phthalid (DE-A 16 43 347);Propamocarb, 3- (dimethylamino) propylcarbamic acid isopropyl ester (DE-A 1567 169); Phthalide (DE-A 16 43 347);
Toloclofos-methyl, O-2,6-Dichlor-p-tolyl O,O-dimethyl phosphorothioat (GB 14 67 561);Toloclofos-methyl, O-2,6-dichloro-p-tolyl O, O-dimethyl phosphorothioate (GB 14 67 561);
Quintozen, Pentachlornitrobenzol (DE-A 682 048);Quintoene, pentachloronitrobenzene (DE-A 682 048);
Zoxamid, (RS)-3,5-Dichlor-N-(3-chlor-1 -ethyl-1 -methyl-2-oxopropyl)-p-toluamid [CASZoxamide, (RS) -3,5-dichloro-N- (3-chloro-1-ethyl-1-methyl-2-oxopropyl) -p-toluamide [CAS
RN 156052-68-5]; Captafol, N-(1,1 ,2,2-Tetrachlorethylthio)cyclohex-4-en-1 ,2-dicarboximidRN 156052-68-5]; Captafol, N- (1,1,2,2-tetrachloroethylthio) cyclohex-4-ene-1,2-dicarboximide
(Phytopathology 52, S. 754 (1962));(Phytopathology 52, p. 754 (1962));
Captan, N-(Trichlormethylthio)cyclohex-4-en-1 ,2-dicarboximid (US 2,553,770); Dichlofluanid, N-Dichlorfluornnethylthio-N',N'-dinnethyl-N-phenylsulfannid (DE-ACaptan, N- (trichloromethylthio) cyclohex-4-ene-1,2-dicarboximide (US 2,553,770); Dichlofluanid, N-dichlorofluoroethylthio-N ', N'-dinethyl-N-phenylsulfannide (DE-A
11 93 498);11 93 498);
Folpet, N-(Trichlomnethylthio)phthalimid (US 2,553,770);Folpet, N- (trichloromethylthio) phthalimide (US 2,553,770);
Tolylfluanid, N-Dichlorfluomnethylthio-N',N'-dimethyl-N-p-tolylsulfannid (DE-A 11 93 498);Tolylfluanid, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-p-tolylsulfannide (DE-A 11 93 498);
Dimethomorph, 3-(4-Chlorphenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-yl-propenonDimethomorph, 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) -1-morpholin-4-yl-propenone
(EP-A 120 321);(EP-A 120 321);
Flumetover, 2-(3,4-Dimethoxyphenyl)-N-ethyl-α,α,α-trifluor-N-nnethyl-p-toluannidFlumetover, 2- (3,4-dimethoxyphenyl) -N-ethyl-α, α, α-trifluoro-N-methyl-p-toluanide
[AGROW Nr. 243, 22 (1995)]; Flumorph, 3-(4-Fluorphenyl)-3-(3,4-dimethoxyphenyl)-1 -morpholin-4-yl-propenon (EP-A[AGROW No. 243, 22 (1995)]; Flumorph, 3- (4-fluorophenyl) -3- (3,4-dimethoxyphenyl) -1-morpholin-4-yl-propenone (EP-A
860 438);860 438);
4-Difluormethyl-2-methyl-thiazol-5-carbonsäure-N-(4'-brom-biphenyl-2-yl)-amid,4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4'-bromo-biphenyl-2-yl) -amide,
4-Difluormethyl-2-methyl-thiazol-5-carbonsäure-N-(4'-trifluormethyl-biphenyl-2-yl)-amid,4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4'-trifluoromethyl-biphenyl-2-yl) -amide,
4-Difluormethyl-2-methyl-thiazol-5-carbonsäure-N-(4'-chlor-3'-fluor-biphenyl-2-yl)-amid, 3-Difluormethyl-1 -methyl-pyrazol-4-carbonsäure-N-(3',4'-dichlor-4-fluor-biphenyl-2-yl)- amid (WO 03/66610);4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4'-chloro-3'-fluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid N- (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide (WO 03/66610);
3,4-Dichlor-isothiazol-5-carbonsäure-N-(2-cyano-phenyl)-amid (WO 99/24413);3,4-dichloro-isothiazole-5-carboxylic acid N- (2-cyanophenyl) -amide (WO 99/24413);
N-(2-(4-[3-(4-Chlor-phenyl)-prop-2-ynyloxy]-3-methoxy-phenyl)-ethyl)-2-methan- sulfonylamino-3-methyl-butyramid, N-(2-(4-[3-(4-Chlor-phenyl)-prop-2-ynyloxy]-3- methoxy-phenyl)-ethyl)-2-ethansulfonylamino-3-methyl-butyramid (WO 04/49804);N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino-3-methylbutyramide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-ethanesulfonylamino-3-methylbutyramide (WO 04/49804);
3-[5-(4-Chlor-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridin (EP-A 10 35 122);3- [5- (4-Chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine (EP-A 10 35 122);
2-Butoxy-6-iodo-3-propyl-chromen-4-on (WO 03/14103);2-butoxy-6-iodo-3-propyl-chromen-4-one (WO 03/14103);
3-(3-Brom-6-fluor-2-methyl-indol-1 -sulfonyl)-[1 ,2,4]triazol-1 -sulfonsäure-dimethylamid3- (3-Bromo-6-fluoro-2-methylindol-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide
(EP-A 10 31 571); (2-Chlor-5-[1-(3-methyl-benzyloxyimino)-ethyl]-benzyl)-carbaminsäure-methylester,(EP-A 10 31 571); (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methylester,
(2-Chlor-5-[1-(6-methyl-pyridin-2-ylmethoxyimino)-ethyl]-benzyl)-carbaminsäure- methylester (EP-A 12 01 648);(2-Chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) -carbamic acid methyl ester (EP-A 12 01 648);
3-(4-Chlor-phenyl)-3-(2-isopropoxy-carbonylamino-3-methyl-butyrylamino)- propionsäure-methylester (EP-A 10 28 125); Azoxystrobin, 2-{2-[6-(2-Cyano-1 -vinyl-penta-1 ,3-dienyloxy)-pyrimidin-4-yloxy]-phenyl}-Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propionate (EP-A 10 28 125); Azoxystrobin, 2- {2- [6- (2-cyano-1-vinyl-penta-1,3-dienyloxy) -pyrimidin-4-yloxy] -phenyl} -
3-methoxy-acrylsäuremethylester (EP-A 382 375);3-methoxy-acrylic acid methyl ester (EP-A 382 375);
Dimoxystrobin, (E)-2-(Methoxyimino)-N-methyl-2-[α-(2,5-xylyloxy)-o-tolyl]acetamid (EP-Dimoxystrobin, (E) -2- (methoxyimino) -N-methyl-2- [α- (2,5-xylyloxy) -o-tolyl] -acetamide (EP-
A 477 631);A 477 631);
Fluoxastrobin, (E)-{2-[6-(2-Chlorphenoxy)-5-fluorpyrimidin-4-yloxy]phenyl}(5,6-dihydro- 1 ,4,2-dioxazin-3-yl)methanon-O-methyloxim (WO 97/27189);Fluoxastrobin, (E) - {2- [6- (2-chlorophenoxy) -5-fluoropyrimidin-4-yloxy] phenyl} (5,6-dihydro-1,2,2-dioxazin-3-yl) methanone-O methyloxime (WO 97/27189);
Kresoxim-methyl, (E)-Methoxyimino[α-(o-tolyloxy)-o-tolyl]essigsäure-methylester (EP-AKresoxim-methyl, (E) -methoxyimino [α- (o-tolyloxy) -o-tolyl] -acetic acid methyl ester (EP-A
253 213);253 213);
Metominostrobin, (E)-2-(Methoxyimino)-N-methyl-2-(2-phenoxyphenyl)-acetamid (EP-AMetominostrobin, (E) -2- (methoxyimino) -N-methyl-2- (2-phenoxyphenyl) -acetamide (EP-A
398 692); Orysastrobin, (2E)-2-(Methoxyimino)-2-{2-[(3E,5E,6E)-5-(methoxyimino)-4,6-dinnethyl-398 692); Orysastrobin, (2E) -2- (methoxyimino) -2- {2 - [(3E, 5E, 6E) -5- (methoxyimino) -4,6-dinethyl-
2,8-dioxa-3,7-diazanona-3,6-dien-1-yl]phenyl}-N-methylacetamid (WO 97/15552); Picoxystrobin, 3-Methoxy-2-[2-(6-trifluormethyl-pyridin-2-yloxymethyl)-phenyl]-acryl- säure-methylester (EP-A 278 595);2,8-dioxa-3,7-diazanon-3,6-dien-1-yl] phenyl} -N-methylacetamide (WO 97/15552); Picoxystrobin, 3-methoxy-2- [2- (6-trifluoromethylpyridin-2-yloxymethyl) -phenyl] -acrylic acid methyl ester (EP-A 278 595);
Pyraclostrobin, N-{2-[1 -(4-Chlorphenyl)-1 H-pyrazol-3-yloxymethyl]phenyl}(N- methoxy)carbaminsäure-nnethylester (WO 96/01256); Trifloxystrobin, (E)-Methoxyimino-{(E)-α-[1 -(α,α,α-trifluor-m-tolyl)ethylidenaminooxy]-o- tolyl}essigsäure-methylester (EP-A 460 575);Pyraclostrobin, N- {2- [1- (4-chlorophenyl) -1H-pyrazol-3-yloxymethyl] phenyl} (N-methoxy) carbamic acid, n-methyl ester (WO 96/01256); Trifloxystrobin, methyl (E) -methoxyimino {(E) -α- [1- (α, α, α-trifluoro-m-tolyl) ethylideneaminooxy] -o-tolyl} acetate (EP-A 460 575);
2-[ortho-(2,5-Dimethylphenyl-oxynnethylen)phenyl]-3-nnethoxy-acrylsäure-nnethylester2- [ortho- (2,5-dimethylphenyl-oxynnethylen) phenyl] -3-nnethoxy-acrylic acid nnethylester
(EP-A 226 917);(EP-A 226 917);
5-Chlor-7-(4-methyl-piperidin-1 -yl)-6-(2,4,6-trifluor-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyri- midin (WO 98/46608);5-Chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine (WO 98/46608);
3,4-Dichlor-N-(2-cyanophenyl)-isothiazol-5-carbonsäureamid (WO 99/24413);3,4-dichloro-N- (2-cyanophenyl) -isothiazole-5-carboxylic acid amide (WO 99/24413);
Verbindungen der Formel IM (WO 04/049804);Compounds of formula IM (WO 04/049804);
N-(2-(4-[3-(4-Chlor-phenyl)-prop-2-ynyloxy]-3-methoxy-phenyl)-ethyl)-2-methan- sulfonylamino-3-methyl-butyramid und N-(2-(4-[3-(4-Chlor-phenyl)-prop-2-ynyloxy]-3- methoxy-phenyl)-ethyl)-2-ethansulfonylamino-3-methyl-butyrannid (WO 03/66609);N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino-3-methylbutyramide and N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-ethanesulfonylamino-3-methyl-butyrannide (WO 03/66609);
2-Butoxy-6-iodo-3-propyl-chromen-4-on der Formel IV (WO 03/14103);2-butoxy-6-iodo-3-propyl-chromen-4-one of the formula IV (WO 03/14103);
3-(3-Brom-6-fluor-2-methyl-indol-1 -sulfonyl)-[1 ,2,4]triazol-1 -sulfonsäuredimethylamid der Formel V (WO 03/053145);3- (3-bromo-6-fluoro-2-methylindol-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide of the formula V (WO 03/053145);
3-(4-Chlor-phenyl)-3-(2-isopropoxycarbonylamino-3-methyl-butyrylamino)- propansäuremethylester der Formel VI (EP-A 1028125).Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propanoate of the formula VI (EP-A 1028125).
Im Hinblick auf eine Senkung der Aufwandmengen und eine Verbreiterung des Wirkungsspektrums der Wirkstoffe I und Il lagen der vorliegenden Erfindung Mischungen als Aufgabe zugrunde, die bei verringerter Gesamtmenge an ausgebrachten Wirk- Stoffen eine verbesserte Wirkung gegen Schadpilze, insbesondere für bestimmte Indikationen, aufweisen.With a view to reducing the application rates and widening the spectrum of action of the active compounds I and II, the present invention was based on mixtures which have an improved action against harmful fungi, in particular for certain indications, with a reduced total amount of active substances applied.
Demgemäss wurden die eingangs definierten Mischungen der Wirkstoffe I und Il gefunden. Es wurde außerdem gefunden, dass sich bei gleichzeitiger, und zwar gemein- samer oder getrennter Anwendung mindestens einer Verbindung I und von mindestens einem der Wirkstoffe II, oder bei Anwendung der Verbindung(en) I und mindestens einem der Wirkstoffe Il nacheinander, Schadpilze besser bekämpfen lassen als mit den Einzelverbindungen allein (synergistische Mischungen).Accordingly, the mixtures of active ingredients I and II defined above were found. It has also been found that in the case of concomitant use of at least one compound I and of at least one of the active compounds II, or when using the compound (s) I and at least one of the active compounds II in succession, harmful fungi fight better than with the individual compounds alone (synergistic mixtures).
Die Verbindungen I lassen sich als Synergisten für eine Vielzahl verschiedener fungizider Wirkstoffe verwenden. Durch gleichzeitige gemeinsame oder getrennte Anwendung von Verbindung(en) I mit mindestens einem Wirkstoff Il wird die fungizide Wirksamkeit in überadditivem Maße erhöht.The compounds I can be used as synergists for a variety of different fungicidal agents. By simultaneous joint or separate application of compound (s) I with at least one active ingredient II, the fungicidal activity is increased to a superadditive extent.
Die Verbindungen I können in verschiedenen Kristallmodifikationen vorliegen, die sich in der biologischen Wirksamkeit unterscheiden können. In Formel I steht Halogen für Fluor, Chlor, Brom oder Jod, vorzugsweise für Fluor oder Chlor.The compounds I can be present in various crystal modifications, which may differ in their biological activity. In formula I, halogen is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
Ci-C4-Alkyl steht für Methyl, Ethyl, n-Propyl, 1-Methylethyl, n-Butyl, 1-Methylpropyl, 2- Methylpropyl oder 1 ,1-Dimethylethyl, vorzugsweise für Methyl oder Ethyl.C 1 -C 4 -alkyl is methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl, preferably methyl or ethyl.
Ci-Cβ-Alkyl steht für einen Ci-C4-Alkylrest wie vorstehend genannt, oder für n-Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 2,2-Dimethylpropyl, 1-Ethylpropyl, n-Hexyl, 1 ,1-Dimethylpropyl, 1 ,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methyl- pentyl, 4-Methylpentyl, 1 ,1-Dimethylbutyl, 1 ,2-Dimethylbutyl, 1 ,3-Dimethylbutyl, 2,2-Di- methylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1 ,1 ,2-Tri- methylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl-1 -methylpropyl und 1 -Ethyl-2-methyl- propyl, vorzugsweise für einen Ci-C4-Alkylrest wie vorstehend genannt.Ci-Cβ-alkyl is a Ci-C 4 -alkyl radical as mentioned above, or for n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1 - methylpropyl and 1-ethyl-2-methyl-propyl, preferably a Ci-C 4 -alkyl radical as mentioned above.
Ci-C4-Halogenalkyl steht für einen teilweise oder vollständig halogenierten Ci-C4-Alkyl- rest, wobei das/die Halogenatom(e) insbesondere Fluor, Chlor und/oder Brom ist/sind, also z.B. Chlormethyl, Brommethyl, Dichlormethyl, Trichlormethyl, Fluormethyl, Difluor- methyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluormethyl, Chlordifluormethyl, 1- Chlorethyl, 1-Bromethyl, 1-Fluorethyl, 2-Fluorethyl, 2,2-Difluorethyl, 2,2,2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2,2-difluorethyl, 2,2-Dichlor-2-fluorethyl, 2,2,2-Trichlor- ethyl, Pentafluorethyl, Heptafluorpropyl oder Nonafluorbutyl, insbesondere für Halogenmethyl, besonders bevorzugt für CH2-CI, CH(CI)2, CH2F, CH(F)2, CF3, CHFCI, CF2CI oder CF(CI)2, insbesondere CHF2 und CF3.Ci-C 4 haloalkyl is a partially or completely halogenated Ci-C 4 alkyl rest, wherein the / the halogen atom (s), especially fluorine, chlorine and / or bromine is / are eg chloromethyl, bromomethyl, dichloromethyl, Trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloroethyl 2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl, in particular for halomethyl, particularly preferably for CH 2 - CI, CH (CI) 2 , CH 2 F, CH (F) 2 , CF 3 , CHFCI, CF 2 CI or CF (CI) 2 , in particular CHF 2 and CF 3 .
Ci-C6-Halogenalkyl steht für einen teilweise oder vollständig halogenierten Ci-Cβ-Alkyl- rest, wobei das/die Halogenatom(e) insbesondere Fluor, Chlor und/oder Brom ist/sind, also z.B. für einen Ci-C4-Halogenalkylrest wie vorstehend genannt, oder für 5-Fluor- pentyl, 5-Chlorpentyl, 5-Brompentyl, 5-lodpentyl, 5,5,5-Trichlorpentyl, Undecafluor- pentyl, 6-Fluorhexyl, 6-Chlorhexyl, 6-Bromhexyl, 6-lodhexyl, 6,6,6-Trichlorhexyl oder Dodecafluorhexyl, vorzugsweise für einen Ci-C4-Halogenalkylrest.C 1 -C 6 -haloalkyl represents a partially or completely halogenated C 1 -C 6 -alkyl radical, where the halogen atom (s) is, in particular, fluorine, chlorine and / or bromine, ie, for example, a C 1 -C 4 -haloalkyl radical as mentioned above, or for 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, 5,5,5-trichloropentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6- lodhexyl, 6,6,6-trichlorohexyl or Dodecafluorhexyl, preferably a Ci-C 4 haloalkyl group.
Die 3,5-disubstituierten Pyrazolcarbonsäurebiphenylamide der Formel I mit X = Sauerstoff sind z.B. aus der WO 2005/123689, der WO 2005/123690 sowie der älteren deutschen Patentanmeldung Nr. 102005007160.0 bekannt oder können nach den dort be- schriebenen Verfahren hergestellt werden.The 3,5-disubstituted pyrazolecarboxylic acid biphenylamides of formula I where X = oxygen are e.g. WO 2005/123689, WO 2005/123690 and the earlier German Patent Application No. 102005007160.0 are known or can be prepared by the process described there.
Diejenigen Verbindungen I, bei denen X für Schwefel steht, sind beispielsweise durch Schwefelung der entsprechenden Verbindungen I, bei denen X für Sauerstoff steht, herstellbar (vgl. z.B. D. Petrova & K. Jakobcic, Croat. Chem. Acta 48, 49 (1976) sowie die WO 01/42223). Unter den 3,5-disubstituierten Pyrazolcarbonsäurebiphenylamiden I sind einerseits diejenigen bevorzugt, bei denen X Sauerstoff bedeutet.Those compounds I in which X is sulfur can be prepared, for example, by sulfurization of the corresponding compounds I in which X is oxygen (cf., for example, D. Petrova & K. Jakobcic, Croat. Chem. Acta 48, 49 (1976 ) and WO 01/42223). Among the 3,5-disubstituted pyrazolecarboxylic acid biphenylamides I, on the one hand, those in which X is oxygen are preferred.
Andererseits sind diejenigen Verbindungen I bevorzugt, bei denen X für Schwefel steht.On the other hand, those compounds I are preferred in which X is sulfur.
Für die erfindungsgemäßen Mischungen sind Verbindungen der Formel I bevorzugt, bei denen R1 und R2 unabhängig voneinander Cyano, Fluor, Chlor, Methyl, Methoxy oder Trifluormethyl bedeuten, R3 für Fluor, Chlor, Methyl oder Ci-Halogenalkyl und R4 für Wasserstoff oder Halogen stehen.For the mixtures according to the invention compounds of the formula I are preferred in which R 1 and R 2 are independently cyano, fluorine, chlorine, methyl, methoxy or trifluoromethyl, R 3 is fluorine, chlorine, methyl or Ci-haloalkyl and R 4 is hydrogen or halogen.
Besonders bevorzugt sind Verbindungen der Formel I, bei denen R1 und R2 unabhängig voneinander Cyano, Fluor, Chlor oder Methoxy bedeuten und R3 für Fluor, Chlor, Methyl, Fluormethyl, Difluormethyl, Chlorfluormethyl, Chlordifluormethyl, Dichlorfluor- methyl oder Trifluormethyl und R4 für Wasserstoff, Fluor oder Chlor stehen.Particular preference is given to compounds of the formula I in which R 1 and R 2 independently of one another are cyano, fluorine, chlorine or methoxy and R 3 is fluorine, chlorine, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl and R 3 4 represent hydrogen, fluorine or chlorine.
Ganz besonders bevorzugt sind Verbindungen der Formel I bei denen R1 und R2 unabhängig voneinander für Fluor oder Chlor stehen, R3 für Methyl, Fluormethyl, Difluormethyl, Chlorfluormethyl, Chlordifluormethyl, Dichlorfluormethyl oder Trifluormethyl und R4 für Wasserstoff stehen .Very particular preference is given to compounds of the formula I in which R 1 and R 2, independently of one another, are fluorine or chlorine, R 3 is methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl and R 4 is hydrogen.
Besonders bevorzugt sind die in den folgenden Tabellen aufgelisteten Verbindungen Ia.Particular preference is given to the compounds Ia listed in the following tables.
Figure imgf000015_0001
Tabelle A
Figure imgf000015_0001
Table A
Figure imgf000015_0002
Figure imgf000015_0002
Figure imgf000016_0001
Figure imgf000016_0001
Tabelle 1 :Table 1 :
Verbindung 1.1 - 1.20Connection 1.1 - 1.20
Verbindungen der Formel I, in denen R1 Fluor bedeutet und R2 und R3 jeweils für die Bedeutungen in einer Zeile der Tabelle A stehen.Compounds of the formula I in which R 1 is fluorine and R 2 and R 3 are each the meanings in a row of Table A.
Tabelle 2:Table 2:
Verbindung 2.1 - 2.20Connection 2.1 - 2.20
Verbindungen der Formel I, in denen R1 Chlor bedeutet und R2 und R3 jeweils für dieCompounds of formula I in which R 1 is chlorine and R 2 and R 3 are each for the
Bedeutungen in einer Zeile der Tabelle A stehen.Meanings in a row of Table A are.
Tabelle 3:Table 3:
Verbindung 3.1 - 3.20Connection 3.1 - 3.20
Verbindungen der Formel I, in denen R1 Brom bedeutet und R2 und R3 jeweils für dieCompounds of formula I in which R 1 is bromine and R 2 and R 3 are each for the
Bedeutungen in einer Zeile der Tabelle A stehen.Meanings in a row of Table A are.
Tabelle 4:Table 4:
Verbindung 4.1 - 4.20Connection 4.1 - 4.20
Verbindungen der Formel I, in denen R1 Jod bedeutet und R2 und R3 jeweils für dieCompounds of formula I in which R 1 is iodine and R 2 and R 3 are each for the
Bedeutungen in einer Zeile der Tabelle A stehen.Meanings in a row of Table A are.
Tabelle 5:Table 5:
Verbindung 5.1 - 5.20Connection 5.1 - 5.20
Verbindungen der Formel I, in denen R1 Methyl bedeutet und R2 und R3 jeweils für dieCompounds of formula I in which R 1 is methyl and R 2 and R 3 are each for the
Bedeutungen in einer Zeile der Tabelle A stehen.Meanings in a row of Table A are.
Tabelle 6:Table 6:
Verbindung 6.1 - 6.20Connection 6.1 - 6.20
Verbindungen der Formel I, in denen R1 Methoxy bedeutet und R2 und R3 jeweils für die Bedeutungen in einer Zeile der Tabelle A stehen. Tabelle 7:Compounds of the formula I in which R 1 is methoxy and R 2 and R 3 are each the meanings in a row of Table A. Table 7:
Verbindung 7.1 - 7.20Connection 7.1 - 7.20
Verbindungen der Formel I, in denen R1 Trifluormethyl bedeutet und R2 und R3 jeweils für die Bedeutungen in einer Zeile der Tabelle A stehen.Compounds of the formula I in which R 1 is trifluoromethyl and R 2 and R 3 are each the meanings in a row of Table A.
Tabelle 8:Table 8:
Verbindung 8.1 - 8.20Connection 8.1 - 8.20
Verbindungen der Formel I, in denen R1 Trifluormethoxy bedeutet und R2 und R3 jeweils für die Bedeutungen in einer Zeile der Tabelle A stehen.Compounds of the formula I in which R 1 is trifluoromethoxy and R 2 and R 3 are each the meanings in a row of Table A.
Tabelle 9:Table 9:
Verbindung 9.1 - 9.20Connection 9.1 - 9.20
Verbindungen der Formel I, in denen R1 Cyano bedeutet und R2 und R3 jeweils für dieCompounds of the formula I in which R 1 is cyano and R 2 and R 3 are each the same
Bedeutungen in einer Zeile der Tabelle A stehen.Meanings in a row of Table A are.
Tabelle 10:Table 10:
Verbindung 10.1 - 10.20Connection 10.1 - 10.20
Verbindungen der Formel I, in denen R1 Nitro bedeutet und R2 und R3 jeweils für dieCompounds of formula I in which R 1 is nitro and R 2 and R 3 are each for the
Bedeutungen in einer Zeile der Tabelle A stehen.Meanings in a row of Table A are.
Ganz besonders bevorzugte Verbindungen der Formel I sind 1-Methyl-3-trifluormethyl- 1 H-pyrazol-4-carbonsäure-N-(3',5'-dichlorbiphenyl-2-yl)-amid, 1 -Methyl-3-trifluormethyl- 1 H-pyrazol-4-carbonsäure-N-(3',5'-difluorbiphenyl-2-yl)-amid, 1 -Methyl-3-trifluormethyl- 1 H-pyrazol-4-carbonsäure-N-(3'-chlor-5'-fluorbiphenyl-2-yl)-amid, 1 -Methyl-3-trifluor- methyl-1 H-pyrazol-4-carbonsäure-N-(3',5'-bis(trifluormethyl)biphenyl-2-yl)-amid, 1- Methyl-3-difluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',5'-dichlorbiphenyl-2-yl)-amid, 1-Methyl-3-difluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',5'-difluorbiphenyl-2-yl)-amid, 1-Methyl-3-difluormethyl-1 H-pyrazol-4-carbonsäure-N-(3'-chlor-5'-fluorbiphenyl-2-yl)- amid, 1 -Methyl-3-difluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',5'-bis(trifluor- methyl)biphenyl-2-yl)-amid, 1-Methyl-3-fluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',51- difluorbiphenyl-2-yl)-amid, 1 -Methyl-3-difluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',51- difluorbiphenyl-2-yl)-amid, 1 -Methyl-3-trifluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',51- difluorbiphenyl-2-yl)-amid, 1 -Methyl-3-difluormethyl-1 H-pyrazol-4-carbonsäure-N-(3'- chlor-5'-fluorbiphenyl-2-yl)-amid, 1 -Methyl-3-trifluormethyl-1 H-pyrazol-4-carbonsäure- N-(3'-chlor-51-fluorbiphenyl-2-yl)-amid, 1-Methyl-3-fluormethyl-1 H-pyrazol-4- carbonsäure-N-(3'-chlor-51-fluorbiphenyl-2-yl)-amid, 1 ,3-Dimethyl-5-fluor-1 H-pyrazol-4- carbonsäure-N-(3'-chlor-51-fluorbiphenyl-2-yl)-amid, 1 ,3-Dimethyl-5-fluor-1 H-pyrazol-4- carbonsäure-N-(31,51-bis(trifluormethyl)biphenyl-2-yl)-amid, 1 ,3-Dimethyl-5-fluor-1 H- pyrazol-4-carbonsäure-N-(3'-fluor-51-methylbiphenyl-2-yl)-amid, 1 ,3-Dimethyl-5-fluor- 1 H-pyrazol-4-carbonsäure-N-(3'-cyano-5l-fluorbiphenyl-2-yl)-amid und 1 ,3-Dimethyl-5- fluor-1 H-pyrazol-4-carbonsäure-N-(3l,5l-dimethylbiphenyl-2-yl)-amid. Bevorzugt sind Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der A) Azole.Very particularly preferred compounds of the formula I are 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'-dichlorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl 1-H-pyrazole-4-carboxylic acid N- (3 ', 5'-difluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro-5'-fluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'-bis (trifluoromethyl) biphenyl-2 -yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'-dichlorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid N- (3 ', 5'-difluorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro -5'-fluorobiphenyl-2-yl) amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'-bis (trifluoromethyl) biphenyl-2-yl ) -amide, 1-methyl-3-fluoromethyl-1 H-pyrazole-4-carboxylic acid-N- (3 ', 5 1 - difluorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1 H- pyrazole-4-carboxylic acid-N- (3 ', 5 1 - difluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid-N- (3 ', 5 1 - difluorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1 H-pyrazol-4- carboxylic acid N- (3'-chloro-5'-fluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro-5 1 - fluorobiphenyl-2-yl) -amide, 1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro-5 1 -fluorobiphenyl-2-yl) -amide, 1, 3 Dimethyl 5-fluoro-1H-pyrazole-4-carboxylic acid N- (3'-chloro-5 1 -fluorobiphenyl-2-yl) -amide, 1, 3-dimethyl-5-fluoro-1H-pyrazole 4-carboxylic acid-N- (3 1, 5 1 -bis (trifluoromethyl) biphenyl-2-yl) -amide, 1, 3-dimethyl-5-fluoro-1 H- pyrazole-4-carboxylic acid-N- (3 ' -fluoro-5 1 -methylbiphenyl-2-yl) -amide, 1, 3-dimethyl-5-fluoro-1H-pyrazole-4-carboxylic acid N- (3'-cyano-5 l -fluorobiphenyl-2-yl ) -amide and 1, 3-dimethyl-5- fluoro-1 H-pyrazole-4-carboxylic acid-N- (3 l, 5 l -dimethylbiphenyl-2-yl) -amide. Preference is given to mixtures of a compound of the formula I with at least one active compound selected from the group of A) azoles.
Bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der B) Strobilurine.Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of B) strobilurins.
Bevorzugt sind Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der C) Carbonsäureamide.Preference is given to mixtures of a compound of the formula I with at least one active compound selected from the group of C) carboxylic acid amides.
Weiterhin bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der D) Heterocyclischen Verbindungen.Also preferred are mixtures of a compound of the formula I with at least one active compound selected from the group of the D) heterocyclic compounds.
Weiterhin bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindes- tens einem Wirkstoff ausgewählt aus der Gruppe der E) Carbamate.Also preferred are mixtures of a compound of formula I with at least one active ingredient selected from the group of E) carbamates.
Weiterhin bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der F) Sonstigen Fungizide.Also preferred are mixtures of a compound of formula I with at least one active ingredient selected from the group of F) other fungicides.
Weiterhin bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der A) Azole, ausgewählt aus Cypro- conazol, Difenoconazol, Epoxiconazol, Fluquinconazol, Flusilazol, Flutriafol, Metcon- azol, Myclobutanil, Penconazol, Propiconazol, Prothioconazol, Triadimefon, Tria- dimenol, Tebuconazol, Tetraconazol, Triticonazol, Prochloraz, Cyazofamid, Benomyl, Carbendazim und Ethaboxam.Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of A) azoles selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole , Triadimefon, triadoxenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamide, benomyl, carbendazim and ethaboxam.
Besonders bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der A) Azole, ausgewählt aus Cyproconazol, Difenoconazol, Epoxiconazol, Fluquinconazol, Flusilazol, Flutriafol, Metconazol, Myclobutanil, Propiconazol, Prothioconazol, Triadimefon, Triadimenol, Tebuconazol, Tetraconazol, Triticonazol, Prochloraz, Cyazofamid, Benomyl und Carbendazim.Particular preference is also given to mixtures of a compound of the formula I with at least one active ingredient selected from the group of A) azoles selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole , Tetraconazole, triticonazole, prochloraz, cyazofamide, benomyl and carbendazim.
Ganz besonders bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der A) Azole, ausgewählt aus Epoxiconazol, Fluquinconazol, Flutriafol, Metconazol, Tebuconazol, Triticonazol, Prochloraz und Carbendazim.Very particular preference is also given to mixtures of a compound of the formula I with at least one active substance selected from the group of A) azoles selected from epoxiconazole, fluquinconazole, flutriafol, metconazole, tebuconazole, triticonazole, prochloraz and carbendazim.
Bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der B) Strobilurine, ausgewählt aus Azoxystrobin, Dimoxystrobin, Fluoxastrobin, Kresoxim-methyl, Orysastrobin, Picoxystrobin, Pyraclo- strobin und Trifloxystrobin. Besonders bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der B) Strobilurine, ausgewählt aus Kresoxim-methyl, Orysastrobin und Pyraclostrobin.Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group consisting of B) strobilurins selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclobutin 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 consisting of B) strobilurins selected from kresoxim-methyl, orysastrobin and pyraclostrobin.
Ganz besonders bevorzugt sind auch Mischungen einer Verbindung der Formel I mit Pyraclostrobin.Very particular preference is also given to mixtures of a compound of the formula I with pyraclostrobin.
Bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der C) Carbonsäureamide, ausgewählt aus Fen- hexamid, Metalaxyl, Mefenoxam, Ofurace, Dimethomorph, Flumorph, Fluopicolid (Pi- cobenzamid), Zoxamid, Carpropamid und Mandipropamid.Preference is also given to mixtures of a compound of the formula I with at least one active substance selected from the group of C) carboxylic acid amides selected from hexadexamide, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolide (picobenzamide), zoxamide, carpropamide and mandipropamide ,
Besonders bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der C) Carbonsäureamide, ausgewählt aus Fenhexamid, Metalaxyl, Mefenoxam, Ofurace, Dimethomorph, Zoxamid und Carpropamid.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 C) carboxylic acid amides selected from fenhexamide, metalaxyl, mefenoxam, ofurace, dimethomorph, zoxamide and carpropamide.
Bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der D) Heterocylischen Verbindungen, ausgewählt aus Fluazinam, Cyprodinil, Fenarimol, Mepanipyrim, Pyrimethanil, Triforin, Fludi- oxonil, Dodemorph, Fenpropimorph, Tridemorph, Fenpropidin, Iprodion, Vinclozolin, Famoxadon, Fenamidon, Probenazol, 5-Chlor-7-(4-methyl-piperidin-1-yl)-6-(2,4,6- trifluor-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin, Proquinazid, Acibenzolar-S-methyl, Captafol, Folpet, Fenoxanil und Quinoxyfen, insbesondere Fluazinam, Cyprodinil, Fenarimol, Mepanipyrim, Pyrimethanil, Triforin, Fludioxonil, Dodemorph, Fenpropimorph, Tridemorph, Fenpropidin, Iprodion, Vinclozolin, Famoxadon, Fenamidon, Probenazol, Proquinazid, Acibenzolar-S-methyl, Captafol, Folpet, Fenoxanil und Quinoxyfen.Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group consisting of d) heterocyclic compounds selected from fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforin, fludiooxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione , Vinclozolin, famoxadone, fenamidone, probenazole, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [ 1, 5-a] pyrimidine, proquinazide, acibenzolar-S-methyl, captafol, folpet, fenoxanil and quinoxyfen, in particular fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforin, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozolin , Famoxadone, fenamidone, probenazole, proquinazide, acibenzolar-S-methyl, captafol, folpet, fenoxanil and quinoxyfen.
Besonders bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff, ausgewählt aus der Gruppe der D) Heterocyclischen Verbindungen, ausgewählt aus Pyrimethanil, Dodemorph, Fenpropimorph, Tridemorph, Iprodion, Vinclozolin, 5-Chlor-7-(4-methyl-piperidin-1-yl)-6-(2,4,6-trifluor-phenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidin und Quinoxyfen, insbesondere Pyrimethanil, Dodemorph, Fenpropimorph, Tridemorph, Iprodion, Vinclozolin und 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 consisting of d) heterocyclic compounds selected from pyrimethanil, dodemorph, fenpropimorph, tridemorph, iprodione, vinclozoline, 5-chloro-7- (4-methyl) piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine and quinoxyfen, especially pyrimethanil, dodemorph, fenpropimorph, tridemorph , Iprodione, vinclozolin and quinoxyfen.
Bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der E) Carbamate, ausgewählt aus Mancozeb, Metiram, Propineb, Thiram, Iprovalicarb, Flubenthiavalicarb und Propamocarb. Besonders bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der E) Carbamate, ausgewählt aus Mancozeb und Metiram.Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group consisting of E) carbamates selected from 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 E) carbamates selected from mancozeb and metiram.
Bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der F) Sonstigen Fungizide, ausgewählt aus Dithianon, Fentin-Salzen wie Fentin-acetat, Fosetyl, Fosetyl-Aluminium, Phosphoriger Säure und deren Salzen, Chlorthalonil, Dichlofluanid, Thiophanat-Methyl, Kupferacetat, Kupferhydroxid, Kupferoxychlorid, basisches Kupfersulfat, Schwefel, Cymoxanil, Metra- fenon und Spiroxamin.Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of F) other fungicides selected from dithianone, fentin salts such as fentin acetate, fosetyl, fosetyl aluminum, phosphorous acid and their salts, chlorothalonil, dichlofluanide , Thiophanate-methyl, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur, cymoxanil, metrafenone and spiroxamine.
Besonders bevorzugt sind auch Mischungen einer Verbindung der Formel I mit mindestens einem Wirkstoff ausgewählt aus der Gruppe der F) Sonstigen Fungizide, ausgewählt aus Phosphoriger Säure und deren Salzen, Chlorthalonil und Metrafenon.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 F) Other fungicides selected from phosphorous acid and its salts, chlorothalonil and metrafenone.
Bevorzugt sind auch Dreiermischungen einer Verbindung der Formel I mit zwei der obengenannten Wirkstoffe II.Also preferred are tri-mixtures of a compound of the formula I with two of the abovementioned active compounds II.
Bevorzugte Wirkstoffkombinationen sind in den folgenden Tabellen 11 bis 17 auf- geführt:Preferred active substance combinations are listed in the following Tables 11 to 17:
Tabelle 11Table 11
Wirkstoffkombinationen von Verbindungen I mit Wirkstoffen Il der Gruppe A):Active substance combinations of compounds I with active ingredients II of group A):
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000023_0001
Tabelle 12Table 12
Wirkstoffkombinationen von Verbindungen I mit Wirkstoffen Il der Gruppe B):Active substance combinations of compounds I with active ingredients II of group B):
Figure imgf000023_0002
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000023_0002
Figure imgf000024_0001
Figure imgf000025_0001
Tabelle 13Table 13
Wirkstoffkombinationen von Verbindungen I mit Wirkstoffen Il der Gruppe C):Active substance combinations of compounds I with active ingredients II of group C):
Figure imgf000025_0002
Figure imgf000025_0002
Tabelle 14:Table 14:
Wirkstoffkombinationen von Verbindungen I mit Wirkstoffen Il der Gruppe D):Active substance combinations of compounds I with active ingredients II of group D):
Figure imgf000025_0003
Figure imgf000025_0003
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Tabelle 15:Table 15:
Wirkstoffkombinationen von Verbindungen I mit Wirkstoffen Il der Gruppe E):Active substance combinations of compounds I with active ingredients II of group E):
Figure imgf000029_0002
Figure imgf000030_0001
Figure imgf000029_0002
Figure imgf000030_0001
Tabelle 16Table 16
Wirkstoffkombinationen von Verbindungen I mit Wirkstoffen Il der Gruppe F):Active substance combinations of compounds I with active ingredients II of group F):
Figure imgf000030_0002
Figure imgf000030_0002
Figure imgf000031_0001
Figure imgf000031_0001
Tabelle 17Table 17
Wirkstoffkombinationen von Verbindungen I mit zwei Wirkstoffen II:Active substance combinations of compounds I with two active substances II:
Figure imgf000031_0002
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000031_0002
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000060_0001
Die Mischungen aus Verbindung(en) I und mindestens einem der Wirkstoffe II, bzw. die gleichzeitige gemeinsame oder getrennte Verwendung mindestens einer Verbindung I mit mindestens einem der Wirkstoffe II, zeichnen sich aus durch eine hervorragende Wirksamkeit gegen ein breites Spektrum von pflanzenpathogenen Pilzen, insbesondere aus der Klasse der Ascomyceten, Deuteromyceten, Basidiomyceten, Peronospo- romyceten (syn. Oomyceten ). Sie sind zum Teil systemisch wirksam und können im Pflanzenschutz als Blatt-, Beiz- und Bodenfungizide eingesetzt werden. Sie können auch zur Saatgutbehandlung verwendet werden.The mixtures of compound (s) I and at least one of the active compounds II, or the simultaneous joint or separate use of at least one compound I with at least one of the active compounds II, are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Basidiomycetes, Peronospo- romyceten (syn. Oomycetes). They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides. They can also be used for seed treatment.
Besondere Bedeutung haben sie für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen wie Bananen, Baumwolle, Gemüsepflanzen (z.B. Gurken, Bohnen und Kürbisse), Gerste, Gras, Hafer, Kaffee, Kartoffeln, Mais, Obstpflanzen, Reis, Roggen, Soja, Tomaten, Wein, Weizen, Zierpflanzen, Zuckerrohr, sowie an den Samen dieser Pflanzen.They are of particular importance for the control of a variety of fungi on various crops such as bananas, cotton, vegetables (eg cucumbers, beans and pumpkins), barley, grass, oats, coffee, potatoes, corn, fruit plants, rice, rye, soy, tomatoes , Wine, wheat, ornamentals, sugarcane, as well as the seeds of these plants.
Speziell eignen sie sich zur Bekämpfung folgender Pflanzenkrankheiten:In particular, they are suitable for controlling the following plant diseases:
Alternaria Arten an Gemüse, Raps, Zuckerrüben und Obst und Reis, z.B. A. solani oder A. alternata an Kartoffeln und Tomaten, - Aphanomyces Arten an Zuckerrüben und Gemüse,Alternaria species on vegetables, rapeseed, sugar beets and fruits and rice, e.g. A. solani or A. alternata on potatoes and tomatoes, - Aphanomyces species on sugar beet and vegetables,
Ascochyta Arten an Getreide and Gemüse,Ascochyta species on cereals and vegetables,
Bipolaris und Drechslera Arten an Mais, Getreide, Reis und Rasen, z.B. D. maydis an Mais,Bipolaris and Drechslera species on corn, cereals, rice and turf, e.g. D. maydis on corn,
Blumeria graminis (Echter Mehltau) an Getreide, - Botrytis cinerea (Grauschimmel) an Erdbeeren, Gemüse, Blumen und Weinreben,Blumeria graminis (powdery mildew) on cereals, - Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and vines,
Bremia lactucae an Salat,Bremia lactucae on salad,
Cercospora Arten an Mais, Sojabohnen, Reis und Zuckerrüben,Cercospora species on maize, soybeans, rice and sugar beet,
Cochliobolus Arten an Mais, Getreide, Reis, z.B. Cochliobolus sativus an Getreide,Cochliobolus species on maize, cereals, rice, e.g. Cochliobolus sativus on cereals,
Cochliobolus miyabeanus an Reis, Colletotricum Arten an Sojabohnen und Baumwolle,Cochliobolus miyabeanus on rice, Colletotricum species on soybeans and cotton,
Drechslera Arten, Pyrenophora Arten an Mais, Getreide, Reis und Rasen, z.B. D. teres an Gerste oder D. tritici-repentis an Weizen,Drechslera species, Pyrenophora species on corn, cereals, rice and turf, e.g. D. teres to barley or D. tritici-repentis to wheat,
Esca an Weinrebe, verursacht durch Phaeoacremonium chlamydosporium, Ph. Aleophilum und Formitipora punctata (syn. Phellinus punctatus ),Esca on grapevine caused by Phaeoacremonium chlamydosporium, Ph. Aleophilum and Formitipora punctata (syn. Phellinus punctatus),
Exserohilum Arten an Mais,Exserohilum species on corn,
Erysiphe cichoracearum und Sphaerotheca fuliginea an Gurkengewächsen,Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
Fusarium und Verticillium Arten an verschiedenen Pflanzen, z.B. F. graminearum oder F. culmorum an Getreide oder F. oxysporum an einer Vielzahl von Pflanzen, z.B. Tomaten,Fusarium and Verticillium species on various plants, e.g. F. graminearum or F. culmorum on cereal or F. oxysporum on a variety of plants, e.g. Tomatoes,
Gaeumanomyces graminis an Getreide,Gaeumanomyces graminis on cereals,
Gibberella Arten an Getreide und Reis (z.B. Gibberella fujikuroi an Reis),Gibberella species on cereals and rice (e.g., Gibberella fujikuroi on rice),
Grainstaining complex an Reis,Grainstaining complex on rice,
Helminthosporium Arten an Mais und Reis, - Michrodochium nivale an Getreide,Helminthosporium species on maize and rice, - Michrodochium nivale on cereals,
Mycosphaerella Arten an Getreide, Bananen und Erdnüssen, z.B. M. graminicola an Weizen oder M. fijiesis an Bananen,Mycosphaerella species on cereals, bananas and peanuts, e.g. M. graminicola on wheat or M. fijiesis on bananas,
Peronospora-Arten an Kohl und Zwiebelgewächsen, z.B. P. brassicae an Kohl oder P. destructor an Zwiebel, - Phakopsara pachyrhizi und Phakopsara meibomiae an Sojabohnen,Peronospora species on cabbage and bulbous plants, e.g. P. brassicae on cabbage or P. destructor on onion, - Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans,
Phomopsis Arten an Sojabohnen und Sonnenblumen,Phomopsis species on soybeans and sunflowers,
Phytophthora infestans an Kartoffeln und Tomaten,Phytophthora infestans on potatoes and tomatoes,
Phytophthora Arten an verschiedenen Pflanzen, z.B. P. capsici an Paprika,Phytophthora species on various plants, e.g. P. capsici on paprika,
Plasmopara viticola an Weinreben, - Podosphaera leucotricha an Apfel,Plasmopara viticola on vines, - Podosphaera leucotricha on vines,
Pseudocercosporella herpotrichoides an Getreide,Pseudocercosporella herpotrichoides on cereals,
Pseudoperonospora an verschiedenen Pflanzen, z.B. P. cubensis an Gurke oderPseudoperonospora on various plants, e.g. P. cubensis on cucumber or
P. humili an Hopfen,P. humili on hops,
Puccinia Arten an verschiedenen Pflanzen, z.B. P. triticina , P. striformins , P. hordei oder P. graminis an Getreide oder P. asparagi an Spargel,Puccinia species on various plants, e.g. P. triticina, P. striformins, P. hordei or P. graminis on cereals or P. asparagi on asparagus,
Pyricularia oryzae , Corticium sasakii , Sarocladium oryzae, S. attenuatum, Enty- loma oryzae an Reis,Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entlyoma oryzae on rice,
Pyricularia grisea an Rasen und Getreide,Pyricularia grisea on lawn and cereals,
Pythium spp. an Rasen, Reis, Mais, Baumwolle, Raps, Sonnenblumen, Zuckerrü- ben, Gemüse und anderen Pflanzen, z.B. P. ultiumum an verschiedenen Pflanzen, P. aphanidermatum an Rasen,Pythium spp. on turf, rice, maize, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants, e.g. P. ultiumum on various plants, P. aphanidermatum on lawn,
Rhizoctonia Arten an Baumwolle, Reis, Kartoffeln, Rasen, Mais, Raps, Zuckerrüben, Gemüse und an verschiedenen Pflanzen, z.B. R. solani an Rüben und verschiedenen Pflanzen, - Rhynchosporium secalis an Gerste, Roggen und Triticale,Rhizoctonia species on cotton, rice, potatoes, turf, corn, rapeseed, sugar beets, vegetables and on various plants, e.g. R. solani on beets and various plants, - Rhynchosporium secalis on barley, rye and triticale,
Sclerotinia Arten an Raps und Sonnenblumen,Sclerotinia species on oilseed rape and sunflowers,
Septoria tritici und Stagonospora nodorum an Weizen, Erysiphe (syn. Uncinula) necator an Weinrebe, Setospaeria Arten an Mais und Rasen, Sphacelotheca reilinia an Mais, Thievaliopsis Arten an Sojabohnen und Baumwolle, - Tilletia Arten an Getreide,Septoria tritici and Stagonospora nodorum on wheat, Erysiphe (Syn. Uncinula) necator on grapevine, Setospaeria species on maize and turf, Sphacelotheca reilinia on maize, Thievaliopsis species on soybean and cotton, - Tilletia species on cereals,
Ustilago Arten an Getreide, Mais und Zuckerrohr, z.B. U. maydis an Mais, Venturia Arten (Schorf) an Äpfeln und Birnen, z.B. V. inaequalis an Apfel.Ustilago species on cereals, maize and sugarcane, e.g. U. maydis on corn, Venturia species (scab) on apples and pears, e.g. V. inaequalis to apple.
Die erfindungsgemäßen Mischungen eignen sich außerdem zur Bekämpfung von Schadpilzen im Materialschutz (z.B. Holz, Papier, Dispersionen für den Anstrich,The mixtures according to the invention are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions,
Fasern bzw. Gewebe) und im Vorratsschutz. Im Holzschutz finden insbesondere folgende Schadpilze Beachtung: Ascomyceten wie Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriel- Ia spp., Trichurus spp.; Basidiomyceten wie Coniophora spp., Coriolus spp., Gloeophyl- lum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. und Tyromyces spp., Deuteromyceten wie Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoder- ma spp., Alternaria spp., Paecilomyces spp. und Zygomyceten wie Mucor spp., darüber hinaus im Materialschutz folgende Hefepilze: Candida spp. und Saccharomyces cerevisae.Fibers or fabrics) and in the storage protection. In wood preservation, particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriela spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophlum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderm spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.
Die Mischungen werden angewendet, indem man die Pilze oder die vor Pilzbefall zu schützenden Pflanzen, Saatgüter, Materialien oder den Erdboden mit einer fungizid wirksamen Menge der Wirkstoffe behandelt. Die Anwendung kann sowohl vor als auch nach der Infektion der Materialien, Pflanzen oder Samen durch die Pilze erfolgen.The mixtures are applied by treating the fungi or the plants, seeds, materials or soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients. The application can be done both before and after the infection of the materials, plants or seeds by the fungi.
Die Verbindung(en) I mit mindestens einem der Wirkstoffe Il können gleichzeitig, und zwar gemeinsam oder getrennt, oder nacheinander aufgebracht werden, wobei die Reihenfolge bei getrennter Applikation im allgemeinen keine Auswirkung auf den Bekämpfungserfolg hat.The compound (s) I with at least one of the active ingredients II can be applied simultaneously, namely jointly or separately, or in succession, the sequence in the case of separate application generally having no effect on the control result.
Bevorzugt setzt man bei der Bereitstellung der Mischungen die reinen Wirkstoffe I bis Il ein, denen man weitere Wirkstoffe gegen Schadpilze oder gegen andere Schädlinge wie Insekten, Spinntiere oder Nematoden oder auch herbizide oder wachstumsregulierende Wirkstoffe oder Düngemittel beimischen kann.The pure active substances I to II are preferably used in the preparation of the mixtures, to which other active substances can be added against harmful fungi or against other pests such as insects, spider animals or nematodes or else herbicidal or growth-regulating active substances or fertilizers.
Derartige Mischungen aus drei Wirkstoffen bestehen z.B. aus einer Verbindung der Formel I, insbesondere 1-Methyl-3-trifluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',51- difluorbiphenyl-2-yl)-amid, 1 -Methyl-3-trifluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',51- dichlorbiphenyl-2-yl)-amid, 1 -Methyl-3-difluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',51- difluorbiphenyl-2-yl)-amid oder 1-Methyl-3-difluormethyl-1 H-pyrazol-4-carbonsäure-N- (S'.δ'-dichlorbiphenyl^-yO-amid, einem Azol aus der Gruppe A), insbesondere Epoxi- conazol, Metconazol, Triticonazol oder Fluquinconazol, und einem Insektizid, wobei insbesondere Fipronil und Neonicotinoide wie Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid und Thiamethoxam in Betracht kommen.Such mixtures of three active substances consist of a mixture of a compound of formula I, particularly 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid-N- (3 ', 5 1 - difluorobiphenyl-2-yl) -amide, 1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5 1 -dichlorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4 carboxylic acid-N- (3 ', 5 1 - difluorobiphenyl-2-yl) amide or 1-methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid-N- (S'.δ'-dichlorobiphenyl ^ -yō amide, an azole from group A), in particular epoxiconazole, metconazole, triticonazole or fluquinconazole, and an insecticide, wherein especially fipronil and neonicotinoids such as acetamipride, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam.
Üblicherweise kommen Mischungen aus mindestens einer Verbindung I und mindes- tens einem Wirkstoff Il zur Anwendung. Dabei können auch Mischungen aus mindestens einer Verbindung I mit zwei oder gewünschtenfalls mehreren Aktivkomponenten besondere Vorteile bieten.Usually, mixtures of at least one compound I and at least one active ingredient II are used. In this case, mixtures of at least one compound I with two or, if desired, several active components can also offer particular advantages.
Als weitere Aktivkomponenten im voranstehenden Sinne kommen besonders die ein- gangs genannten Wirkstoffe Il und insbesondere die voranstehend genannten bevorzugten Wirkstoffe Il in Betracht.Suitable further active components in the above sense are, in particular, the aforementioned active compounds II and in particular the above-mentioned preferred active compounds II.
Verbindung(en) I und Wirkstoff(e) Il werden üblicherweise in einem Gewichtsverhältnis von 100:1 bis 1 :100, vorzugsweise 20:1 bis 1 :20, insbesondere 10:1 bis 1 :10, ange- wandt.Compound (s) I and active compound (II) II are usually used 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.
Die weiteren Aktivkomponenten werden gewünschtenfalls im Verhältnis von 20:1 bis 1 :20 zu der Verbindung I gemischt.If desired, the further active components are mixed in a ratio of from 20: 1 to 1:20 to give compound I.
Die Aufwandmengen der erfindungsgemäßen Mischungen liegen, vor allem bei landwirtschaftlichen Kulturflächen, je nach Art der Verbindungen I und Il sowie des gewünschten Effekts, bei 5 g/ha bis 2000 g/ha, vorzugsweise 20 bis 1500 g/ha, insbesondere 50 bis 1000 g/ha.The application rates of the mixtures according to the invention, especially in agricultural crops, depending on the nature of the compounds I and II and the desired effect, at 5 g / ha to 2000 g / ha, preferably 20 to 1500 g / ha, in particular 50 to 1000 g /Ha.
Die Aufwandmengen für die Verbindung(en) I liegen entsprechend in der Regel bei 1 bis 1000 g/ha, vorzugsweise 10 bis 900 g/ha, insbesondere 20 bis 750 g/ha.The application rates for the compound (s) I are accordingly generally 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 20 to 750 g / ha.
Die Aufwandmengen für die Wirkstoffe Il liegen entsprechend in der Regel bei 1 bis 2000 g/ha, vorzugsweise 1 bis 1500 g/ha, insbesondere 40 bis 1000 g/ha.The application rates for the active ingredients II are correspondingly generally 1 to 2000 g / ha, preferably 1 to 1500 g / ha, in particular 40 to 1000 g / ha.
Bei der Saatgutbehandlung werden im allgemeinen Aufwandmengen an Mischung von 1 bis 1000 g pro 100 kg Saatgut, vorzugsweise 1 bis 750 g pro 100 kg, insbesondere 5 bis 500 g pro 100 kg Saatgut, verwendet.In the seed treatment, application rates of mixture of 1 to 1000 g per 100 kg of seed, preferably 1 to 750 g per 100 kg, in particular 5 to 500 g per 100 kg of seed are generally used.
Das Verfahren zur Bekämpfung von Schadpilzen erfolgt durch die getrennte oder gemeinsame Applikation von Verbindung(en) I und mindestens einem der Wirkstoffe II, oder einer Mischung aus Verbindung(en) I und mindestens einem der Wirkstoffe II, durch Besprühen oder Bestäuben der Samen, der Pflanzen oder der Böden vor oder nach der Aussaat der Pflanzen oder vor oder nach dem Auflaufen der Pflanzen.The method for controlling harmful fungi is carried out by the separate or combined application of compound (s) I and at least one of the active compounds II, or a mixture of compound (s) I and at least one of the active ingredients II, by spraying or dusting the seeds, the Plants or soils before or after sowing the plants or before or after emergence of the plants.
Die erfindungsgemäßen fungiziden synergistischen Mischungen, bzw. die Verbindungen) I und mindestens einer der Wirkstoffe II, können in die üblichen Formulierun- gen übergeführt werden, z.B. Lösungen, Emulsionen, Suspensionen, Stäube, Pulver, Pasten und Granulate. Die Anwendungsform richtet sich nach dem jeweiligen Verwendungszweck; sie soll in jedem Fall eine möglichst feine und gleichmäßige Verteilung der erfindungsgemäßen Mischung gewährleisten.The fungicidal synergistic mixtures according to the invention, or the compounds I and at least one of the active compounds II, can be converted into the customary formulations. be transferred, for example, solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; It should in any case ensure the finest possible and uniform distribution of the mixture according to the invention.
Die Formulierungen werden in an sich bekannter Weise hergestellt, z.B. durch Verstrecken der Wirkstoffe mit Lösungsmitteln und/oder Trägerstoffen, gewünschtenfalls unter Verwendung von Emulgiermitteln und Dispergiermitteln. Als Lösungsmittel / Hilfs- stoffe kommen dafür im wesentlichen in Betracht: - Wasser, aromatische Lösungsmittel (z.B. Solvesso® Produkte, XyIoI), ParaffineThe formulations are prepared in a manner known per se, for example by stretching the active compounds with solvents and / or excipients, if desired using emulsifiers and dispersants. Solvents / auxiliary materials which are suitable are essentially: - water, aromatic solvents (for example Solvesso ® products, xylene), paraffins
(z.B. Erdölfraktionen), Alkohole (z.B. Methanol, Butanol, Pentanol, Benzylalkohol), Ketone (z.B. Cyclohexanon, gamma-Butryolacton), Pyrrolidone (N-Methyl- pyrrolidon, N-Octylpyrrolidon), Acetate (Glykoldiacetat), Glykole, Dimethylfettsäu- reamide, Fettsäuren und Fettsäureester. Grundsätzlich können auch Lösungsmit- telgemische verwendet werden.(eg, petroleum fractions), alcohols (eg, methanol, butanol, pentanol, benzyl alcohol), ketones (eg, cyclohexanone, gamma-butyrolactone), pyrrolidones (N-methylpyrrolidone, N-octylpyrrolidone), acetates (glycol diacetate), glycols, dimethyl fatty acid amides , Fatty acids and fatty acid esters. In principle, solvent mixtures can also be used.
Trägerstoffe wie natürliche Gesteinsmehle (z.B. Kaoline, Tonerden, Talkum, Kreide) und synthetische Gesteinsmehle (z.B. hochdisperse Kieselsäure, Silikate); Emulgiermittel wie nichtionogene und anionische Emulgatoren (z.B. Polyoxyethy- len-Fettalkohol-Ether, Alkylsulfonate und Arylsulfonate) und Dispergiermittel wie Lignin-Sulfitablaugen und Methylcellulose.Carriers such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.
Als oberflächenaktive Stoffe kommen Alkali-, Erdalkali-, Ammoniumsalze von Ligninsul- fonsäure, Naphthalinsulfonsäure, Phenolsulfonsäure, Dibutylnaphthalinsulfonsäure, Alkylarylsulfonate, Alkylsulfate, Alkylsulfonate, Fettalkoholsulfate, Fettsäuren und sulfa- tierte Fettalkoholglykolether zum Einsatz, ferner Kondensationsprodukte von sulfonier- tem Naphthalin und Naphthalinderivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphtalinsulfonsäure mit Phenol und Formaldehyd, Polyoxyethy- lenoctylphenolether, ethoxyliertes Isooctylphenol, Octylphenol, Nonylphenol, Alkylphe- nolpolyglykolether, Tributylphenylpolyglykolether, Tristerylphenylpolyglykolether, Alkyl- arylpolyetheralkohole, Alkohol- und Fettalkoholethylenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether, ethoxyliertes Polyoxypropylen, Laurylalkoholpoly- glykoletheracetal, Sorbitester, Ligninsulfitablaugen und Methylcellulose in Betracht.The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.
Zur Herstellung von direkt versprühbaren Lösungen, Emulsionen, Pasten oder Öl- dispersionen kommen Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Toluol, XyIoI, Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, Methanol, Ethanol, Propanol, Butanol, Cyclohexanol, Cyclohexanon, Isophoron, stark pola- re Lösungsmittel, z.B. Dimethylsulfoxid, N-Methylpyrrolidon oder Wasser, in Betracht. Pulver-, Streu- und Stäubmittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit mindestens einem festen Trägerstoff hergestellt werden.For the production of directly sprayable solutions, emulsions, pastes or oil dispersions come mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg toluene, xylene, paraffin, Tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water into consideration. Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with at least one solid carrier.
Granulate, z.B. Umhüllungs-, Imprägnierungs- oder Homogengranulate, können durch Bindung der Wirkstoffe an mindestens einen festen Trägerstoff hergestellt werden. Feste Trägerstoffe sind beispielsweise Mineralerden wie Kieselgele, Silikate, Talkum, Kaolin, Attaclay, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel wie Ammonium-sulfat, Ammoniumphosphat, Ammonium nitrat, Harnstoffe und pflanzliche Produkte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulose- pulver oder andere feste Trägerstoffe.Granules, e.g. Coated, impregnated or homogeneous granules may be prepared by binding the active ingredients to at least one solid carrier. Solid carriers are, for example, mineral soils such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
Die Formulierungen enthalten im allgemeinen 0,01 bis 95 Gew.-%, vorzugsweise 0,1 bis 90 Gew.-%, der Verbindung(en) I und mindestens einem der Wirkstoffe Il bzw. der Mischung aus Verbindung(en) I mit mindestens einem der Wirkstoffe II. Die Wirkstoffe werden dabei in einer Reinheit von 90% bis 100%, vorzugsweise 95% bis 100%, (nach NMR- oder HPLC-Spektrum) eingesetzt.The formulations generally contain from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the compound (s) I and at least one of the active compounds II or of the mixture of compound (I) I with at least one of the active ingredients II. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR or HPLC spectrum).
Beispiele für Formulierungen sind: 1. Produkte zur Verdünnung in WasserExamples of formulations are: 1. Products for dilution in water
A) Wasserlösliche Konzentrate (SL)A) Water Soluble Concentrates (SL)
10 Gew.-Teile einer erfindungsgemäßen Mischung werden mit 90 Gew.-Teilen Wasser oder einem wasserlöslichen Lösungsmittel gelöst. Alternativ werden Netzmittel oder andere Hilfsmittel zugefügt. Bei der Verdünnung in Wasser löst sich der Wirkstoff. Man erhält auf diese Weise eine Formulierung mit einem Wirkstoffgehalt von 10 Gew.-%.10 parts by weight of a mixture according to the invention are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with an active substance content of 10% by weight.
B) Dispergierbare Konzentrate (DC) 20 Gew.-Teile einer erfindungsgemäßen Mischung werden in 70 Gew.-Teilen Cyclohe- xanon unter Zusatz von 10 Gew.-Teilen eines Dispergiermittels, z.B. Polyvinylpyrroli- don, gelöst. Bei Verdünnung in Wasser ergibt sich eine Dispersion. Der Wirkstoffgehalt beträgt 20 Gew.-%.B) Dispersible Concentrates (DC) 20 parts by weight of a mixture according to the invention are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersing agent, e.g. Polyvinylpyrrolidone, dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight.
C) Emulgierbare Konzentrate (EC)C) Emulsifiable Concentrates (EC)
15 Gew.-Teile einer erfindungsgemäßen Mischung werden in 75 Gew.-Teilen XyIoI unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxylat (jeweils 5 Gew.- Teile) gelöst. Bei der Verdünnung in Wasser ergibt sich eine Emulsion. Die Formulierung hat einen Wirkstoffgehalt von 15 Gew.-%.15 parts by weight of a mixture according to the invention 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 in water results in an emulsion. The formulation has an active ingredient content of 15% by weight.
D) Emulsionen (EW, EO)D) Emulsions (EW, EO)
25 Gew.-Teile einer erfindungsgemäßen Mischung werden in 35 Gew.-Teilen XyIoI unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxylat (jeweils 5 Gew.- Teile) gelöst. Diese Mischung wird mittels einer Emulgiermaschine (z.B. Ultraturrax) in 30 Gew. Teile Wasser gegeben und zu einer homogenen Emulsion gebracht. Bei der Verdünnung in Wasser ergibt sich eine Emulsion. Die Formulierung hat einen Wirk- stoffgehalt von 25 Gew.-%.25 parts by weight of a mixture according to the invention are in 35 parts by weight of XyIoI with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added by means of an emulsifying machine (eg Ultraturrax) in 30 parts by weight of water and brought to a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.
E) Suspensionen (SC, OD)E) suspensions (SC, OD)
20 Gew.-Teile einer erfindungsgemäßen Mischung werden unter Zusatz von 10 Gew.- Teilen Dispergier- und Netzmitteln und 70 Gew. -Teilen Wasser oder einem organi- sehen Lösungsmittel in einer Rührwerkskugelmühle zu einer feinen Wirkstoffsuspension zerkleinert. Bei der Verdünnung in Wasser ergibt sich eine stabile Suspension des Wirkstoffs. Der Wirkstoffgehalt in der Formulierung beträgt 20 Gew.-%.20 parts by weight of a mixture according to the invention are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight.
F) Wasserdispergierbare und wasserlösliche Granulate (WG, SG) 50 Gew.-Teile einer erfindungsgemäßen Mischung werden unter Zusatz von 50 Gew- Teilen Dispergier- und Netzmitteln fein gemahlen und mittels technischer Geräte (z.B. Extrusion, Sprühturm, Wirbelschicht) als wasserdispergierbare oder wasserlösliche Granulate hergestellt. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs. Die Formulierung hat einen Wirkstoffgehalt von 50 Gew.- %.F) Water-dispersible and Water-soluble Granules (WG, SG) 50 parts by weight of a mixture according to the invention are finely ground with the addition of 50 parts by weight dispersing and wetting agents and by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules produced. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight.
G) Wasserdispergierbare und wasserlösliche Pulver (WP, SP)G) Water-dispersible and water-soluble powders (WP, SP)
75 Gew.-Teile einer erfindungsgemäßen Mischung werden unter Zusatz von 25 Gew.- Teilen Dispergier- und Netzmitteln sowie Kieselsäuregel in einer Rotor-Strator Mühle vermählen. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs. Der Wirkstoffgehalt der Formulierung beträgt 75 Gew.-%.75 parts by weight of a mixture according to the invention are ground with the addition of 25 parts by weight of dispersants and wetting agents and silica gel in a rotor-Strator mill. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.
2. Produkte für die Direktapplikation2. Products for direct application
H) Stäube (DP)H) dusts (DP)
5 Gew.-Teile einer erfindungsgemäßen Mischung werden fein gemahlen und mit 95 Gew.-Teilen feinteiligem Kaolin innig vermischt. Man erhält dadurch ein Stäubemittel mit einem Wirkstoffgehalt von 5 Gew.-%.5 parts by weight of a mixture according to the invention are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with an active ingredient content of 5 wt .-%.
J) Granulate (GR, FG, GG, MG)J) Granules (GR, FG, GG, MG)
0,5 Gew-Teile einer erfindungsgemäßen Mischung werden fein gemahlen und mit 99,5 Gew.-Teilen Trägerstoffe verbunden. Gängige Verfahren sind dabei die Extrusion, die Sprühtrocknung oder die Wirbelschicht. Man erhält dadurch ein Granulat für die Direktapplikation mit einem Wirkstoffgehalt von 0,5 Gew.-%.0.5 parts by weight of a mixture according to the invention are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with an active ingredient content of 0.5 wt .-%.
K) ULV- Lösungen (UL)K) ULV solutions (UL)
10 Gew.-Teile einer erfindungsgemäßen Mischung werden in 90 Gew.-Teilen eines organischen Lösungsmittel, z.B. XyIoI, gelöst. Dadurch erhält man ein Produkt für die Direktapplikation mit einem Wirkstoffgehalt von 10 Gew.-%.10 parts by weight of a mixture according to the invention are in 90 parts by weight of a organic solvents, eg xylene, dissolved. This gives a product for direct application with an active ingredient content of 10 wt .-%.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus berei- teten Anwendungsformen, z.B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen oder Dispersionen, Emulsionen, Öldispersionen, Pasten, Stäubmitteln, Streumitteln, Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der Wirk- Stoffe gewährleisten.The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active substances.
Wässrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netzbaren Pulvern (Spritzpulver, Öldispersionen) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Öldispersionen können die Sub- stanzen als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermitttel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.
Die Wirkstoffkonzentrationen in den anwendungsfertigen Zubereitungen können in größeren Bereichen variiert werden. Im allgemeinen liegen sie zwischen 0,0001 und 10%, vorzugsweise zwischen 0,01 und 1 %.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%.
Die Wirkstoffe können auch mit gutem Erfolg im Ultra-Low-Volume-Verfahren (ULV) verwendet werden, wobei es möglich ist, Formulierungen mit mehr als 95 Gew.-% Wirkstoff oder sogar den Wirkstoff ohne Zusätze auszubringen.The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.
Zu den Wirkstoffen können Öle verschiedenen Typs, Netzmittel, Adjuvants, Herbizide, andere Schädlingsbekämpfungsmittel, Bakterizide, gewünschtenfalls auch erst unmittelbar vor der Anwendung (Tankmix), zugesetzt werden. Diese Mittel werden üblicherweise zu den erfindungsgemäßen Mischungen im Gewichtsverhältnis 1 :100 bis 100:1 , bevorzugt 1 :10 bis 10:1 , zugemischt.To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, other pesticides, bactericides, if desired, also just immediately before use (tank mix), can be added. These agents are usually admixed to the mixtures according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.
Als Adjuvants in diesem Sinne kommen insbesondere in Frage: organisch modifizierte Polysiloxane, z.B. Break Thru S 240®; Alkoholalkoxylate, z. B. Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® und Lutensol ON 30®; EO-PO-Blockpolymerisate, z. B. Pluro- nic RPE 2035® und Genapol B®; Alkoholethoxylate, z. B. Lutensol XP 80®; und Natri- umdioctylsulfosuccinat, z. B. Leophen RA®.As adjuvants in this sense are in particular: organically modified polysiloxanes, eg Break Thru S 240 ® ; Alcohol alkoxylates, eg. As Atplus 245 ®, Atplus MBA 1303 ®, Plurafac LF 300 ® and Lutensol ON 30 ®; EO-PO block polymers, eg. B. Pluro- nic RPE 2035 ® and Genapol B ®; Alcohol ethoxylates, eg. As Lutensol XP 80 ®; and sodium dioctylsulfosuccinate, e. B. Leophen RA ®.
Die Verbindungen I und II, bzw. die Mischungen oder die entsprechenden Formulierungen werden angewendet, indem man die Schadpilze, deren Lebensraum oder die von ihnen freizuhaltenden Pflanzen, Samen, Böden, Flächen, Materialien oder Räume mit einer fungizid wirksamen Menge der Mischung, bzw. der Verbindungen I und Il bei getrennter Ausbringung, behandelt. Die Anwendung kann vor oder nach dem Befall durch die Schadpilze erfolgen.The compounds I and II, or the mixtures or the corresponding formulations are applied by the harmful fungi, their habitat or the treated plants, seeds, soils, areas, materials or spaces with a fungicidally effective amount of the mixture, or the compounds I and II with separate application treated. The application can be made before or after the attack by the harmful fungi.
HerstellungsbeispielePreparation Examples
1.) Synthese von ortho-(3,5-Dichlophenyl)-anilin1.) Synthesis of ortho- (3,5-dichlorophenyl) -aniline
Zu einer Lösung von 20,47 g 2-Bromanilin, 24,98 g 3,5-Dichlorphenylboronsäure und 25,23 g Natriumcarbonat in einer Mischung von 150 ml Wasser und 450 ml Ethylengly- coldimethylether wurden 1 ,4 g Tetrakistriphenylphosphin-Palladium(O) gegeben. Man rührte 23 Std. unter Rückfluß. Der Ansatz wurde bei reduziertem Druck eingeengt. Der Rückstand wurde mit Methyl-tert.-butylether aufgenommen und dreimal mit Wasser gewaschen, über Natriumsulfat getrocknet und bei reduziertem Druck eingeengt. Nach chromatographischer Reinigung mit einer Mischung von Toluol und Cyclohexan (1 :4) erhielt man 13,3 g des Produktes als weißes Pulver.To a solution of 20.47 g of 2-bromoaniline, 24.98 g of 3,5-dichlorophenylboronic acid and 25.23 g of sodium carbonate in a mixture of 150 ml of water and 450 ml of ethylene glycol dimethyl ether, 1.4 g of tetrakistriphenylphosphine palladium (O ). The mixture was stirred for 23 hours under reflux. The batch was concentrated under reduced pressure. The residue was taken up with methyl tert-butyl ether and washed three times with water, dried over sodium sulfate and concentrated under reduced pressure. After chromatographic purification with a mixture of toluene and cyclohexane (1: 4) gave 13.3 g of the product as a white powder.
2.) Synthese von 1-Methyl-3-trifluormethyl-N-(ortho-(3,5-dichlorphenyl)phenyl)-pyrazol- 4-carbonsäureamid.2.) Synthesis of 1-methyl-3-trifluoromethyl-N- (ortho- (3,5-dichlorophenyl) phenyl) -pyrazole-4-carboxylic acid amide.
In 350 ml Toluol wurden 9,88 g 1-Methyl-3-trifluormethyl-pyrazol-4-carbonsäurechlorid, 11 ,07 g ortho-(3,5-Dichlorphenyl)anilin und 5,52 g Pyridin gelöst. Nachdem 48 Std. bei Raumtemperatur gerührt wurde, gab man 400 ml Methyl-tert-butylether zu. Anschließend wurde die Reaktionsmischung zweimal mit 5%iger Salzsäure, einmal mit 5%iger Natronlauge und zweimal mit Wasser gewaschen. Die organische Phase wurde über Natriumsulfat getrocknet und bei reduziertem Druck eingeengt. Das Rohprodukt wurde aus Diisopropylether umkristallisiert und mit n-Pentan gewaschen. Dabei erhielt man 16,94 g des Produktes als farbloses Pulver; Fp.: 101-1050C.In 350 ml of toluene, 9.88 g of 1-methyl-3-trifluoromethyl-pyrazole-4-carbonyl chloride, 11, 07 g of ortho- (3,5-dichlorophenyl) aniline and 5.52 g of pyridine were dissolved. After stirring at room temperature for 48 hours, 400 ml of methyl tert-butyl ether were added. Subsequently, the reaction mixture was washed twice with 5% hydrochloric acid, once with 5% sodium hydroxide solution and twice with water. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. The crude product was recrystallized from diisopropyl ether and washed with n-pentane. This gave 16.94 g of the product as a colorless powder; Mp .: 101-105 0 C.
In der nachfolgenden Tabelle 18 sind neben der vorstehend beschriebenen Verbindung beispielhaft noch weitere 3,5-disubstituierte Pyrazolcarbonsäurebiphenylamide der Formel I, wobei X für Sauerstoff steht, aufgelistet, die auf die gleiche Weise hergestellt wurden oder herstellbar sind.In the following Table 18, in addition to the compound described above, further 3.5-disubstituted pyrazolecarboxylic acid biphenylamides of the formula I in which X is oxygen are listed by way of example, which have been prepared or can be prepared in the same way.
Tabelle 18Table 18
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000068_0001
Figure imgf000069_0001
Anwendungsbeispielexample
Die synergistische Wirkung der erfindungsgemäßen Mischungen ließ sich durch die folgenden Versuche zeigen:The synergistic effect of the mixtures according to the invention was demonstrated by the following experiments:
Die Wirkstoffe wurden getrennt oder gemeinsam als eine Stammlösung aufbereitet mit 25 mg Wirkstoff, welcher mit einem Gemisch aus Aceton und/oder Dimethylsulfoxid und dem Emulgator Uniperol® EL (Netzmittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxylierter Alkylphenole) im Volumen-Verhältnis Lösungsmittel-Emulgator von 99 zu 1 ad 10 ml aufgefüllt wurde. Anschließend wurde ad 100 ml mit Wasser aufgefüllt. Diese Stammlösung wurde mit dem beschriebenen Lösungsmittel-Emulgator-Wasser Gemisch zu der unten angegebenen Wirkstoffkonzentration verdünnt.The active compounds were prepared separately or together as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or dimethyl sulfoxide and the emulsifier Uniperol ® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent- Emulsifier from 99 to 1 ad 10 ml was filled. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.
Alternativ dazu wurden die Wirkstoffe Epoxiconazol und Pyraclostrobin als handelsübliche Fertigformulierung verwendet und mit Wasser auf die angegebenen Wirkstoffkonzentrationen verdünnt. Die visuell ermittelten Werte für den Prozentanteil befallener Blattflächen wurden in Wirkungsgrade als % der unbehandelten Kontrolle umgerechnet.Alternatively, the active ingredients epoxiconazole and pyraclostrobin were used as a commercially available ready-made formulation and diluted with water to the stated active substance concentrations. The visually determined values for the percentage of affected leaf areas were converted into efficiencies as% of the untreated control.
Der Wirkungsgrad (W) wurde nach der Formel von Abbot wie folgt bestimmt:The efficiency (W) was determined according to the formula of Abbot as follows:
W = (1 - α / ß) « 100W = (1 - α / β) «100
α entspricht dem Pilzbefall der behandelten Pflanzen in % und ß entspricht dem Pilzbefall der unbehandelten (Kontroll-) Pflanzen in %α corresponds to the fungal infestation of the treated plants in% and β corresponds to the fungal infestation of the untreated (control) plants in%
Bei einem Wirkungsgrad von 0 entspricht der Befall der behandelten Pflanzen demjenigen der unbehandelten Kontrollpflanzen; bei einem Wirkungsgrad von 100 wiesen die behandelten Pflanzen keinen Befall auf.With an efficiency of 0, the infestation of the treated plants corresponds to that of the untreated control plants; at an efficiency of 100, the treated plants had no infestation.
Die zu erwartenden Wirkungsgrade der Wirkstoffmischungen wurden nach der Colby Formel [R.S. Colby, „Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds ^5, 20-22 (1967)] ermittelt und mit den beobachteten Wirkungsgraden verglichen.The expected efficiencies of the drug mixtures were determined by Colby's formula [R.S. Colby, "Calculating synergistic and antagonistic responses of herbicidal combinations", Weeds ^ 5, 20-22 (1967)] and compared with the observed efficiencies.
Colby Formel: E = x + y - x°y / 100Colby formula: E = x + y - x ° y / 100
E zu erwartender Wirkungsgrad, ausgedrückt in % der unbehandelten Kontrolle, beim Einsatz der Mischung aus den Wirkstoffen A und B in den Konzentrationen a und b; x der Wirkungsgrad, ausgedrückt in % der unbehandelten Kontrolle, beim Einsatz des Wirkstoffs A in der Konzentration a; y der Wirkungsgrad, ausgedrückt in % der unbehandelten Kontrolle, beim Einsatz des Wirkstoffs B in der Konzentration b.E expected efficiency, expressed as% of untreated control, when using the mixture of Active Agents A and B at concentrations a and b; x the efficiency, expressed in% of the untreated control, when using active substance A at concentration a; y the efficiency, expressed in% of the untreated control, when using active substance B in concentration b.
Anwendungsbeispiel 1 - Wirksamkeit gegen die Dürrfleckenkrankheit der Tomate verursacht durch Alternaria solaniUse Example 1 - Efficacy against tomato blight caused by Alternaria solani
Blätter von getopften Tomatenpflanzen wurden mit einer wässriger Suspension in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe besprüht. Am folgenden Tag wurden die Blätter mit einer wässrigen Sporenaufschwemmung von Alternaria solani in 2 % Biomalzlösung mit einer Dichte von 0.17 x 106 Sporen/ml infiziert. Anschließend wurden die Pflanzen in einer wasserdampf-gesättigten Kammer bei Temperaturen zwischen 20 und 220C aufgestellt. Nach 5 Tagen hatte sich die Krankheit auf den unbehandelten, jedoch infizierten Kontrollpflanzen so stark entwickelt, dass der Befall visuell in % ermittelt werden konnte. Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the drug concentration below. The following day, the leaves were infected with an aqueous spore suspension of Alternaria solani in 2% biomalt solution with a density of 0.17 × 10 6 spores / ml. The plants were then placed in a water vapor-saturated chamber at temperatures between 20 and 22 0 C. After 5 days, the disease on the untreated, but infected control plants had developed so strongly that the infestation could be determined visually in%.
Figure imgf000071_0001
Figure imgf000071_0001
Anwendungsbeispiel 2 - Wirksamkeit gegen den Grauschimmel an Paprikablättern verursacht durch Botrytis cinerea bei 1 Tag protektiver AnwendungApplication Example 2 - Activity against gray mold on pepper leaves caused by Botrytis cinerea at 1 day of protective application
Paprikasämlinge der Sorte "Neusiedler Ideal Elite" wurden, nachdem sich 2 - 3 Blätter gut entwickelt hatten, mit einer wässrigen Suspension in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe besprüht. Am nächsten Tag wurden die behandelten Pflanzen mit einer Sporensuspension von Botrytis cinerea, die 1.7 x 106 Sporen/ml in einer 2 %igen wässrigen Biomalzlösung enthielt, inokuliert. Anschließend wurden die Versuchspflanzen in eine Klimakammer mit 22 bis 240C, Dunkelheit und hoher Luftfeuchtigkeit gestellt. Nach 5 Tagen konnte das Ausmaß des Pilzbefalls auf den Blättern visuell in % ermittelt werden.Paprika seedlings of the cultivar "Neusiedler Ideal Elite" were sprayed to drip point with an aqueous suspension in the concentration of active compound stated below, after 2-3 leaves had developed well. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 10 6 spores / ml in a 2% aqueous biomalt solution. Subsequently, the test plants were placed in a climatic chamber with 22 to 24 0 C, darkness and high humidity. After 5 days, the extent of fungal attack on the leaves could be determined visually in%.
Figure imgf000071_0002
Figure imgf000071_0002
Anwendungsbeispiel 3 - Wirksamkeit gegen Weizenmehltau verursacht durch Erysiphe [syn. Blumeria] graminis fomna specialis. triticiUse Example 3 - Activity against wheat powdery mildew caused by Erysiphe [syn. Blumeria] graminis fomna specialis. tritici
Blätter von in Töpfen gewachsenen Weizenkeimlingen wurden mit wässriger Suspension in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe besprüht. Die Suspension oder Emulsion wurde wie oben beschrieben hergestellt. 24 Stunden nach dem Antrocknen des Spritzbelages mit Sporen des Weizenmehltaus (Erysiphe [syn. Blumeria] graminis fomna specialis. tritici) bestäubt. Die Versuchspflanzen wurden anschließend im Gewächshaus bei Temperaturen zwischen 20 und 24°C und 60 bis 90 % relativer Luftfeuchtigkeit aufgestellt. Nach 7 Tagen wurde das Ausmaß der Mehltauentwicklung visuell in % Befall der gesamten Blattfläche ermittelt.Leaves of potted wheat seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. The suspension or emulsion was prepared as described above. 24 hours after the spray coating has dried on spores of wheat powdery mildew (Erysiphe [syn. graminis fomna specialis. tritici) pollinated. The test plants were then placed in a greenhouse at temperatures between 20 and 24 ° C and 60 to 90% relative humidity. After 7 days, the extent of mildew development was determined visually in% infestation of the entire leaf area.
Figure imgf000072_0001
Figure imgf000072_0001
Anwendungsbeispiel 4 - Protektive Wirksamkeit gegen Puccinia recondita an Weizen (Weizenbraunrost)Use Example 4 Protective Activity Against Puccinia recondita on Wheat (Wheat Brown Rust)
Blätter von in Töpfen gewachsenen Weizensämlingen der Sorte "Kanzler" wurden mit einer wässriger Suspension in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe besprüht. Am nächsten Tag wurden die behandelten Pflanzen mit einer Sporensuspension des Weizenbraunrostes (Puccinia recondita) inokuliert. Anschließend wurden die Pflanzen für 24 Stunden in eine Kammer mit hoher Luftfeuchtigkeit (90 bis 95 %) bei 20 bis 220C gestellt. Während dieser Zeit keimten die Sporen aus und die Keimschläuche drangen in das Blattgewebe ein. Am folgenden Tag wurden die Versuchspflanzen ins Gewächshaus zurückgestellt und bei Temperaturen zwischen 20 und 220C und 65 bis 70 % relativer Luftfeuchte für weitere 7 Tage kultiviert. Dann wurde das Ausmaß der Rostpilzentwicklung auf den Blättern visuell ermittelt.Leaves of potted wheat seedlings of the variety "Chancellor" were sprayed to drip point with an aqueous suspension in the active ingredient concentration given below. The next day, the treated plants were inoculated with a spore suspension of the wheat brown rust (Puccinia recondita). Subsequently, the plants were placed in a high humidity chamber (90 to 95%) at 20 to 22 ° C. for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The following day, the test plants were returned to the greenhouse and cultured at temperatures between 20 and 22 0 C and 65 to 70% relative humidity for a further 7 days. Then the extent of rust fungus development on the leaves was visually determined.
Figure imgf000072_0002
Anwendungsbeispiel 5 - Kurative Wirksamkeit gegen Sojarost verursacht durch Pha- kopsora pachyrhizi
Figure imgf000072_0002
Example of Use 5 - Curative efficacy against soybean rust caused by Phokopsora pachyrhizi
Blätter von in Töpfen gewachsenen Sojasämlingen der Sorte „Oxford" wurden mit einer Sporensuspension des Sojarostes (Phakopsora pachyrhizi) inokuliert. Danach wurden die Töpfe für 24 Stunden in eine Kammer mit hoher Luftfeuchtigkeit (90 bis 95 %) und 23 bis 27°C gestellt. Während dieser Zeit keimten die Sporen aus und die Keimschläuche drangen in das Blattgewebe ein. Die infizierten Pflanzen wurden nach 2 Tagen mit der oben beschriebenen Wirkstoff lösung in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe besprüht. Nach dem Antrocknen des Spritzbelages wurden die Versuchspflanzen im Gewächshaus bei Temperaturen zwischen 23 und 27°C und 60 bis 80 % relativer Luftfeuchte für 14 Tage kultiviert. Dann wurde das Ausmaß der Rostpilzentwicklung auf den Blättern ermittelt.Leaves of potted "Oxford" soybean seedlings were inoculated with a spore suspension of soybean rust (Phakopsora pachyrhizi) and then placed in a high humidity chamber (90-95%) and 23-27 ° C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue.The infected plants were sprayed to drip point after 2 days with the above-described active ingredient solution in the below-specified active ingredient concentration Temperatures between 23 and 27 ° C and 60 to 80% relative humidity were cultivated for 14 days, then the extent of rust fungus development on the leaves was determined.
Figure imgf000073_0001
Figure imgf000073_0001

Claims

Patentansprüche claims
1. Fungizide Mischungen zur Bekämpfung von pflanzenpathogenen Schadpilzen, enthaltend1. Fungicidal mixtures for controlling phytopathogenic harmful fungi, containing
1) mindestens ein 3,5-disubstituiertes Pyrazolcarbonsäurebiphenylamid der Formel I1) at least one 3,5-disubstituted pyrazolecarboxylic acid biphenylamide of the formula I
Figure imgf000074_0001
in der die Substituenten folgende Bedeutungen haben: X Sauerstoff oder Schwefel; R1 und R2 unabhängig voneinander Cyano, Nitro, Halogen, Ci-Cβ-Alkyl, Ci-Cβ-
Figure imgf000074_0001
in which the substituents have the following meanings: X is oxygen or sulfur; R 1 and R 2 independently of one another cyano, nitro, halogen, Ci-Cβ-alkyl, Ci-Cβ-
Halogenalkyl, Methoxy, Difluormethoxy oder Trifluormethoxy; R3 Halogen, CrC4-AIkVl oder Ci-C4-Halogenalkyl; R4 Wasserstoff oder Halogen; undHaloalkyl, methoxy, difluoromethoxy or trifluoromethoxy; R 3 is halogen, -C 4 -alkyl or Ci-C 4 haloalkyl; R 4 is hydrogen or halogen; and
2) mindestens einen Wirkstoff Il ausgewählt aus den Gruppen A) bis F):2) at least one active ingredient II selected from the groups A) to F):
A) Azole ausgewählt aus Bitertanol, Bromuconazol, Cyproconazol, Difeno- conazol, Diniconazol, Enilconazol, Epoxiconazol, Fluquinconazol, Fen- buconazol, Flusilazol, Flutriafol, Hexaconazol, Imibenconazol, Ipconazol,A) azoles selected from bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole,
Metconazol, Myclobutanil, Penconazol, Propiconazol, Prothioconazol, Simeconazol, Triadimefon, Triadimenol, Tebuconazol, Tetraconazol, Triticonazol, Prochloraz, Pefurazoat, Imazalil, Triflumizol, Cyazofamid, Benomyl, Carbendazim, Thiabendazol, Fuberidazol, Ethaboxam, Etridiazol und Hymexazol;Metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, triadimefon, triadimol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamide, benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole and hymexazole;
B) Strobilurine ausgewählt aus Azoxystrobin, Dimoxystrobin, Enestroburin, Fluoxastrobin, Kresoxim-methyl, Methominostrobin, Orysastrobin, Pico- xystrobin, Pyraclostrobin, Trifloxystrobin, Enestroburin, (2-Chlor-5-[1-(3- methyl-benzyloxyimino)-ethyl]-benzyl)-carbaminsäure-methylester,B) strobilurins selected from azoxystrobin, dimoxystrobin, enestroburine, fluoxastrobin, kresoxim-methyl, methominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburine, (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl ] benzyl) -carbamic acid methylester,
(2-Chlor-5-[1-(6-methyl-pyridin-2-ylmethoxyimino)-ethyl]-benzyl)-carb- aminsäure-methylester und 2-(ortho-(2,5-Dimethylphenyl-oxymethylen)- phenyl)-3-methoxy-acrylsäure-methylester;(2-Chloro-5- [1- (6-methyl-pyridin-2-ylmethoxyimino) -ethyl] -benzyl) -carbamic acid methyl ester and 2- (ortho- (2,5-dimethylphenyl-oxymethylene) -phenyl ) -3-methoxy-acrylic acid methylester;
C) Carbonsäureamide ausgewählt aus Carboxin, Benalaxyl, Boscalid, Fen- hexamid, Flutolanil, Furametpyr, Mepronil, Metalaxyl, Mefenoxam, Ofurace, Oxadixyl, Oxycarboxin, Penthiopyrad, Thifluzamid, Tiadinil, 3,4-Dichlor-N-(2-cyanophenyl)-isothiazol-5-carbonsäureamid, Dimethomorph, Flumorph, Flumetover, Fluopicolid (Picobenzamid), Zo- xamid, Carpropamid, Diclocymet, Mandipropamid, N-(2-(4-[3-(4-Chlor- phenyl)-prop-2-ynyloxy]-3-methoxy-phenyl)-ethyl)-2-methansulfonyl- amino-3-methyl-butyrannid, N-(2-(4-[3-(4-Chlor-phenyl)-prop-2-ynyloxy]-3- methoxy-phenyl)-ethyl)-2-ethansulfonylamino-3-nnethyl-butyrannid, 3-(4-Chlor-phenyl)-3-(2-isopropoxy-carbonylamino-3-methyl-butyryl- amino)-propionsäure-methylester, Verbindungen der Formel IMC) Carboxylic acid amides selected from carboxin, benalaxyl, boscalid, hexadexamide, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxine, penthiopyrad, thifluzamide, tiadinil, 3,4-Dichloro-N- (2-cyanophenyl) -isothiazole-5-carboxylic acid amide, dimethomorph, flumorph, flumetover, fluopicolide (picobenzamide), zooxamide, carpropamide, diclocymet, mandipropamide, N- (2- [4-] 3- (4-chlorophenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino-3-methylbutyrannide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-ethanesulfonylamino-3-n-ethyl-butyrannide, 3- (4-chloro-phenyl) -3- (2- isopropoxycarbonylamino-3-methyl-butyryl-amino) -propionic acid methyl ester, compounds of the formula III
Figure imgf000075_0001
in der R5 Methyl oder Ethyl bedeutet;
Figure imgf000075_0001
in which R 5 is methyl or ethyl;
4-Difluormethyl-2-methyl-thiazol-5-carbonsäure-N-(4'-brom-biphenyl-2-yl)- amid, 4-Difluormethyl-2-methyl-thiazol-5-carbonsäure-N-(4'-trifluormethyl- biphenyl-2-yl)-amid, 4-Difluormethyl-2-methyl-thiazol-5-carbonsäure-N-(4'- chlor-3'-fluor-biphenyl-2-yl)-amid, 3-Difluormethyl-1-methyl-pyrazol-4- carbonsäure-N-(3',4'-dichlor-4-fluor-biphenyl-2-yl)-amid und 3,4-Dichlor- isothiazol-5-carbonsäure-N-(2-cyano-phenyl)-amid;4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4'-bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4 ' -trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4'-chloro-3'-fluorobiphenyl-2-yl) -amide, 3 Difluoromethyl-1-methyl-pyrazole-4-carboxylic acid N- (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide and 3,4-dichloro-isothiazole-5-carboxylic acid-N- (2-cyano-phenyl) -amide;
D) Heterocyclische Verbindungen ausgewählt aus Fluazinam, Pyrifenox, Bupirimat, Cyprodinil, Fenarimol, Ferimzon, Mepanipyrim, Nuarimol, Pyrimethanil, Triforin, Fenpiclonil, Fludioxonil, Aldimorph, Dodemorph, Fenpropimorph, Tridemorph, Fenpropidin, Iprodion, Procymidon, Vin- clozolin, Famoxadon, Fenamidon, Octhilinon, Probenazol, 5-Chlor-7-(4- methyl-piperidin-1 -yl)-6-(2,4,6-trifluor-phenyl)-[1 ,2,4]triazolo[1 ,5- ajpyrimidin, Anilazin, Diclomezin, Pyroquilon, Proquinazid, Tricyclazol, die Verbindu men-4-on)D) Heterocyclic compounds selected from fluazinam, pyrifenox, bupirimat, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil, triforin, fenpiclonil, fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone, vanadiumzolin, famoxadone, Fenamidone, octhilinone, probenazole, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1, 5 ajpyrimidine, anilazine, diclomethine, pyroquilon, proquinazide, tricyclazole, the compounds 4-one)
Figure imgf000075_0002
Figure imgf000075_0002
Acibenzolar-S-methyl, Captafol, Captan, Dazomet, Folpet, Fenoxanil, Quinoxyfen und 3-(3-Brom-6-fluor-2-methyl-indol-1-sulfonyl)-[1 ,2,4]triazol-Acibenzolar-S-methyl, captafol, captan, dazomet, folpet, fenoxanil, quinoxyfen and 3- (3-bromo-6-fluoro-2-methyl-indole-1-sulfonyl) - [1, 2,4] triazole
1-sulfonsäu1-sulfonic
Figure imgf000075_0003
E) Carbamate ausgewählt aus Mancozeb, Maneb, Metam, Metiram, Ferbam, Propineb, Thiram, Zineb, Ziram, Diethofencarb, Iprovalicarb, Flubenthiavalicarb, Propamocarb, N-(1 -(1 -(4-cyanophenyl)ethansulfonyl)- but-2-yl)-carbaminsäure-(4-fluorphenyl)ester, 3-(4-Chlor-phenyl)-3-(2- isopropoxy-carbonylamino-3-methyl-butyrylannino)-propansäure- methylester der Formel VI
Figure imgf000075_0003
E) Carbamates selected from Mancozeb, Maneb, Metam, Metiram, Ferbam, Propineb, Thiram, Zineb, Ziram, Diethofencarb, Iprovalicarb, Flubenthiavalicarb, Propamocarb, N- (1- (1 - (4-cyanophenyl) ethanesulfonyl) - but-2 -yl) -carbamic acid (4-fluorophenyl) ester, 3- (4-chloro-phenyl) -3- (2-isopropoxy-carbonylamino-3-methyl-butyrylannino) -propanoic acid methyl ester of the formula VI
Figure imgf000076_0001
und Carbamatoximether der Formel VII
Figure imgf000076_0001
and carbamato oxime ethers of formula VII
Figure imgf000076_0002
in der Z für N oder CH steht;
Figure imgf000076_0002
Z is N or CH;
F) Sonstige Fungizide, ausgewählt aus Guanidine: Dodin, Iminoctadin, Guazatin, Antibiotika: Kasugamycin, Streptomycin, Polyoxin, Validamycin A, Nitrophenylderivate: Binapacryl, Dinocap, Dinobuton,F) Other fungicides selected from guanidines: dodin, iminoctadine, guazatine, antibiotics: kasugamycin, streptomycin, polyoxin, validamycin A, nitrophenyl derivatives: binapacryl, dinocap, dinobuton,
Schwefelhaltige Heterocyclylverbindungen: Dithianon, Isoprothiolan, Organometallverbindungen: Fentin-Salze wie Fentin-acetat, Organophosphorverbindungen: Edifenphos, Iprobenfos, Fosetyl, Fosetyl-Aluminium, Phosphorige Säure und deren Salze, Pyrazophos, Tolclofos-methyl,Sulfur-containing heterocyclyl compounds: dithianone, isoprothiolane, organometallic compounds: fentin salts such as fentin acetate, organophosphorus compounds: edifenphos, Iprobenfos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl,
Organochlorverbindungen: Chlorthalonil, Dichlofluanid, Flusulfamid,Organochlorine compounds: chlorothalonil, dichlofluanid, flusulfamide,
Hexachlorbenzol, Phthalid, Pencycuron, Quintozen, Thiophanat-Methyl,Hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate-methyl,
Tolylfluanid,tolylfluanid,
Anorganische Wirkstoffe: Bordeaux Brühe, Kupferacetat, Kupferhydroxid, Kupferoxychlorid, basisches Kupfersulfat, Schwefel,Inorganic active ingredients: Bordeaux broth, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur,
Sonstige: Cyflufenamid, Cymoxanil, Dimethirimol, Ethirimol, Furalaxyl, Metrafenon und Spiroxamin;Other: Cyflufenamid, Cymoxanil, Dimethirimol, Ethirimol, Furalaxyl, Metrafenone and Spiroxamine;
in einer synergistisch wirksamen Menge.in a synergistically effective amount.
2. Fungizide Mischungen nach Anspruch 1, enthaltend als Komponente 1) ein 3,5- disubstituiertes Pyrazolcarbonsäurebiphenylamid der Formel I, in der R1 und R2 unabhängig voneinander für Cyano, Fluor, Chlor, Methyl, Methoxy oder Trifluor- methyl, R3 für Fluor, Chlor, Methyl oder Ci-Halogenalkyl und R4 für Wasserstoff oder Halogen stehen. 2. Fungicidal mixtures according to claim 1, comprising as component 1) a 3,5-disubstituted pyrazolecarboxylic acid biphenylamide of the formula I in which R 1 and R 2 independently of one another are cyano, fluorine, chlorine, methyl, methoxy or trifluoromethyl, R 3 are fluorine, chlorine, methyl or Ci-haloalkyl and R 4 is hydrogen or halogen.
3. Fungizide Mischungen nach Anspruch 1, enthaltend als Komponente 1) ein 3,5- disubstituiertes Pyrazolcarbonsäurebiphenylamid der Formel I, in der R1 und R2 unabhängig voneinander für Cyano, Fluor, Chlor oder Methoxy, R3 für Fluor, Chlor, Methyl, Fluormethyl, Difluormethyl, Chlorfluormethyl, Chlordifluormethyl, Dichlorfluormethyl oder Trifluormethyl und R4 für Wasserstoff, Fluor oder Chlor stehen.3. Fungicidal mixtures according to claim 1, comprising as component 1) a 3,5-disubstituted Pyrazolcarbonsäurebiphenylamid of formula I, wherein R 1 and R 2 are independently cyano, fluoro, chloro or methoxy, R 3 is fluorine, chlorine, methyl , Fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl and R 4 are hydrogen, fluorine or chlorine.
4. Fungizide Mischungen nach Anspruch 1, enthaltend als Komponente 1) ein 3,5- disubstituiertes Pyrazolcarbonsäurebiphenylamid der Formel I, in der die S übst i- tuenten R1 und R2 unabhängig voneinander für Fluor oder Chlor, R3 für Methyl,4. Fungicidal mixtures according to claim 1, comprising as component 1) a 3,5-disubstituted pyrazolecarboxylic acid biphenylamide of the formula I in which the substituents R 1 and R 2 independently of one another are fluorine or chlorine, R 3 is methyl,
Fluormethyl, Difluormethyl, Chlorfluormethyl, Chlordifluormethyl, Dichlorfluormethyl oder Trifluormethyl und R4 für Wasserstoff stehen.Fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl and R 4 are hydrogen.
5. Fungizide Mischungen nach Anspruch 1, enthaltend als Komponente 1) 1 -Methyl-3-trifluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',5'-dichlorbiphenyl-2-yl)- amid, 1 -Methyl-3-trifluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',5'-difluor- biphenyl-2-yl)-amid, 1 -Methyl-3-trifluormethyl-1 H-pyrazol-4-carbonsäure-N-(3'- chlor-5'-fluorbiphenyl-2-yl)-amid, 1 -Methyl-3-trifluormethyl-1 H-pyrazol-4-carbon- säure-N-(3',5'-bis(trifluormethyl)biphenyl-2-yl)-amid, 1 -Methyl-3-difluormethyl-1 H- pyrazol-4-carbonsäure-N-(3',5'-dichlorbiphenyl-2-yl)-amid, 1 -Methyl-3-difluor- methyl-1 H-pyrazol-4-carbonsäure-N-(3',5'-difluorbiphenyl-2-yl)-amid, 1 -Methyl-3- difluormethyl-1 H-pyrazol-4-carbonsäure-N-(3'-chlor-5'-fluorbiphenyl-2-yl)-amid, 1-Methyl-3-difluormethyl-1 H-pyrazol-4-carbonsäure-N-(3',5'-bis(trifluor- methyl)biphenyl-2-yl)-amid, 1 -Methyl-3-fluormethyl-1 H-pyrazol-4-carbonsäure-N- (S'.δ'-difluorbiphenyl^-yO-amid, 1-Methyl-3-difluormethyl-1 H-pyrazol-4- carbonsäure-N-(31,51-difluorbiphenyl-2-yl)-amid, 1 -Methyl-3-trifluormethyl-1 H- pyrazol-4-carbonsäure-N-(31,51-difluorbiphenyl-2-yl)-amid, 1-Methyl-3- difluormethyl-1 H-pyrazol-4-carbonsäure-N-(3'-chlor-51-fluorbiphenyl-2-yl)-amid, 1 - Methyl-3-trifluormethyl-1 H-pyrazol-4-carbonsäure-N-(3'-chlor-5l-fluorbiphenyl-2- yl)-amid, 1-Methyl-3-fluormethyl-1 H-pyrazol-4-carbonsäure-N-(3'-chlor-51- fluorbiphenyl-2-yl)-amid, 1 ,3-Dimethyl-5-fluor-1 H-pyrazol-4-carbonsäure-N-(3'- chlor-5'-fluorbiphenyl-2-yl)-amid, 1 ,3-Dimethyl-5-fluor-1 H-pyrazol-4-carbonsäure- N-(31,51-bis(trifluormethyl)biphenyl-2-yl)-amid, 1 ,3-Dimethyl-5-fluor-1 H-pyrazol-4- carbonsäure-N-(3'-fluor-51-methylbiphenyl-2-yl)-amid, 1 ,3-Dimethyl-5-fluor-1 H- pyrazol-4-carbonsäure-N-(3'-cyano-51-fluorbiphenyl-2-yl)-amid und 1 ,3-Dimethyl-5. Fungicidal mixtures according to claim 1, comprising as component 1) 1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxylic acid N- (3 ', 5'-dichlorobiphenyl-2-yl) - amide, 1 - Methyl 3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'-difluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4 carboxylic acid N- (3'-chloro-5'-fluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'- bis (trifluoromethyl) biphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'-dichlorobiphenyl-2-yl) -amide, 1 - Methyl 3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'-difluorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4 carboxylic acid N- (3'-chloro-5'-fluorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 5'-bis ( trifluoromethyl) biphenyl-2-yl) -amide, 1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxylic acid N- (S'.δ'-difluorobiphenyl) -yO-amide, 1-methyl- 3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 1 , 5 1 -difluorbi phenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 1 , 5 1 -difluorobiphenyl-2-yl) -amide, 1-methyl-3- difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro-5 1 -fluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro-5 l -fluorobiphenyl-2-yl) -amide, 1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro-5 1 -fluorobiphenyl-2-yl) yl) amide, 1, 3-dimethyl-5-fluoro-1H-pyrazole-4-carboxylic acid N- (3'-chloro-5'-fluorobiphenyl-2-yl) -amide, 1, 3-dimethyl- 5-fluoro-1 H-pyrazole-4-carboxylic acid N- (3 1, 5 1 -bis (trifluoromethyl) biphenyl-2-yl) -amide, 1, 3-dimethyl-5-fluoro-1 H-pyrazol 4-Carboxylic acid N- (3'-fluoro-5 1 -methylbiphenyl-2-yl) -amide, 1, 3-dimethyl-5-fluoro-1H-pyrazole-4-carboxylic acid N- (3'-cyano -5 1 -fluorobiphenyl-2-yl) -amide and 1, 3-dimethyl
5-fluor-1 H-pyrazol-4-carbonsäure-N-(3',5l-dimethylbiphenyl-2-yl)-amid.5-fluoro-1H-pyrazole-4-carboxylic acid N- (3 ', 5 l -dimethylbiphenyl-2-yl) -amide.
6. Fungizide Mischungen nach einem der Ansprüche 1 bis 5, enthaltend die Komponenten 1) und 2) in einem Gewichtsverhältnis von 100:1 bis 1 :100. 6. Fungicidal mixtures according to one of claims 1 to 5, comprising the components 1) and 2) in a weight ratio of 100: 1 to 1: 100.
7. Fungizides Mittel, enthaltend eine fungizide Mischung gemäß den Ansprüchen 1 bis 5 sowie mindestens einen festen oder flüssigen Trägerstoff.7. A fungicidal composition containing a fungicidal mixture according to claims 1 to 5 and at least one solid or liquid carrier.
8. Verfahren zur Bekämpfung von phytopathogenen Schadpilzen, dadurch gekenn- zeichnet, dass man die Schadpilze, deren Lebensraum oder die vor Pilzbefall zu schützenden Pflanzen, den Boden, Saatgüter, Flächen, Materialien oder Räume mit einer fungiziden Mischung gemäß einem der Ansprüche 1 bis 5 behandelt.8. A method for controlling phytopathogenic harmful fungi, characterized in that the harmful fungi, their habitat or the plants to be protected from fungal attack, the soil, seeds, areas, materials or rooms with a fungicidal mixture according to one of claims 1 to 5 treated.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass man die Komponen- ten 1) und 2) gemäß den Ansprüchen 1 bis 5 gleichzeitig, und zwar gemeinsam oder getrennt, oder nacheinander ausbringt.9. The method according to claim 8, characterized in that the components 1) and 2) according to claims 1 to 5 at the same time, jointly or separately, or successively auszustingt.
10. Verfahren nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass man die Komponenten 1) und 2) gemäß den Ansprüchen 1 bis 5 in einer Menge von 5 g/ha bis 2000 g/ha aufwendet.10. The method according to claim 8 or 9, characterized in that the components 1) and 2) according to claims 1 to 5 in an amount of 5 g / ha to 2000 g / ha expends.
11. Verfahren nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass man die Komponenten 1) und 2) gemäß den Ansprüchen 1 bis 5 in einer Menge von 1 g bis 1000 g pro 100 kg Saatgut anwendet.11. The method according to claim 8 or 9, characterized in that applying the components 1) and 2) according to claims 1 to 5 in an amount of 1 g to 1000 g per 100 kg of seed.
12. Saatgut, enthaltend eine Mischung gemäß den Ansprüchen 1 bis 5 in einer Menge von 1 g bis 1000 g pro 100 kg Saatgut.12. Seed containing a mixture according to claims 1 to 5 in an amount of 1 g to 1000 g per 100 kg of seed.
13. Verwendung der Verbindungen I und Il gemäß den Ansprüchen 1 bis 5 zur Her- Stellung eines zur Bekämpfung von Schadpilzen geeigneten Mittels. 13. Use of the compounds I and II according to claims 1 to 5 for the production of a preparation suitable for controlling harmful fungi.
PCT/EP2006/063664 2005-07-01 2006-06-29 Fungicide mixtures based on 3,5-disubstituted pyrazol-carboxylic acid biphenylamides WO2007003564A1 (en)

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US11/988,141 US20090042725A1 (en) 2005-07-01 2006-06-29 Fungicidal Mixtures Based on 3,5-Disubstituted N-Biphenyl-Pyrazolcarboxamides
JP2008518845A JP2009500311A (en) 2005-07-01 2006-06-29 Disinfectant mixture based on 3,5-disubstituted N-biphenylpyrazole carboxamide
BRPI0612804A BRPI0612804A2 (en) 2005-07-01 2006-06-29 fungicidal mixtures to combat phytopathogenic harmful fungi, fungicidal agent, process to combat phytopathogenic harmful fungi, seed, and use of compounds
EP06763960A EP1903867A1 (en) 2005-07-01 2006-06-29 Fungicide mixtures based on 3,5-disubstituted pyrazol-carboxylic acid biphenylamides

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007017416A3 (en) * 2005-08-05 2007-05-10 Basf Ag Fungicidal mixtures containing substituted 1-methyl pyrazol-4-yl carboxylic acid anilides
WO2007110173A2 (en) * 2006-03-24 2007-10-04 Bayer Cropscience Ag Fungicidal active substance combinations
WO2008135480A2 (en) * 2007-05-02 2008-11-13 Basf Se Method for controlling specific fungal pathogen in soybeans by employing benodanil
JP2010517974A (en) * 2007-02-05 2010-05-27 ビーエーエスエフ ソシエタス・ヨーロピア Bactericidal mixture comprising substituted 1-methylpyrazol-4-ylcarboxyanilides
CN103907610A (en) * 2013-01-06 2014-07-09 江苏丰登农药有限公司 Sterilization composition containing fluxapyroxad and picoxystrobin, and application thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997010716A1 (en) * 1995-09-22 1997-03-27 Basf Aktiengesellschaft Harmful fungi control with an active substance inhibiting respiration by inhibiting the cytochrome complex iii, combined with an amide
WO1999031983A1 (en) * 1997-12-18 1999-07-01 Basf Aktiengesellschaft Fungicide mixtures based on pyridine amides and chlorothalonil
WO1999031986A1 (en) * 1997-12-18 1999-07-01 Basf Aktiengesellschaft Fungicide mixtures based on pyride amides and morpholine derivatives or piperidine derivatives
WO1999031979A1 (en) * 1997-12-18 1999-07-01 Basf Aktiengesellschaft Fungicide mixtures based on amide compounds and azoles
WO2005034628A1 (en) * 2003-10-10 2005-04-21 Bayer Cropscience Aktiengesellschaft Synergistic fungicidal active substance combinations
WO2005110089A2 (en) * 2004-05-13 2005-11-24 Basf Aktiengesellschaft Fungicide mixtures made from a triazolopyrimidine derivative and biphenylamides
WO2005123689A1 (en) * 2004-06-18 2005-12-29 Basf Aktiengesellschaft 1-methyl-3-trifluoromethyl-pyrazole-4-carboxylic acid (ortho-phenyl)-anilides and to use thereof as fungicide
WO2005123690A1 (en) * 2004-06-18 2005-12-29 Basf Aktiengesellschaft 1-methyl-3-difluoromethyl-pyrazol-4-carbonic acid-(ortho-phenyl)-anilides, and use thereof as a fungicide
WO2006032356A1 (en) * 2004-09-17 2006-03-30 Bayer Cropscience Ag Synergistic fungicidal active substance combinations which contain spiroxamine, a triazole and a carboxamide

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997010716A1 (en) * 1995-09-22 1997-03-27 Basf Aktiengesellschaft Harmful fungi control with an active substance inhibiting respiration by inhibiting the cytochrome complex iii, combined with an amide
WO1999031983A1 (en) * 1997-12-18 1999-07-01 Basf Aktiengesellschaft Fungicide mixtures based on pyridine amides and chlorothalonil
WO1999031986A1 (en) * 1997-12-18 1999-07-01 Basf Aktiengesellschaft Fungicide mixtures based on pyride amides and morpholine derivatives or piperidine derivatives
WO1999031979A1 (en) * 1997-12-18 1999-07-01 Basf Aktiengesellschaft Fungicide mixtures based on amide compounds and azoles
WO2005034628A1 (en) * 2003-10-10 2005-04-21 Bayer Cropscience Aktiengesellschaft Synergistic fungicidal active substance combinations
WO2005110089A2 (en) * 2004-05-13 2005-11-24 Basf Aktiengesellschaft Fungicide mixtures made from a triazolopyrimidine derivative and biphenylamides
WO2005123689A1 (en) * 2004-06-18 2005-12-29 Basf Aktiengesellschaft 1-methyl-3-trifluoromethyl-pyrazole-4-carboxylic acid (ortho-phenyl)-anilides and to use thereof as fungicide
WO2005123690A1 (en) * 2004-06-18 2005-12-29 Basf Aktiengesellschaft 1-methyl-3-difluoromethyl-pyrazol-4-carbonic acid-(ortho-phenyl)-anilides, and use thereof as a fungicide
WO2006032356A1 (en) * 2004-09-17 2006-03-30 Bayer Cropscience Ag Synergistic fungicidal active substance combinations which contain spiroxamine, a triazole and a carboxamide

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007017416A3 (en) * 2005-08-05 2007-05-10 Basf Ag Fungicidal mixtures containing substituted 1-methyl pyrazol-4-yl carboxylic acid anilides
EA014099B1 (en) * 2005-08-05 2010-08-30 Басф Се Fungicidal mixtures containing substituted 1-methyl pyrazol-4-yl carboxylic acid anilides
US8153819B2 (en) 2005-08-05 2012-04-10 Basf Se Fungicidal mixtures comprising substituted 1-methylpyrazol-4-ylcarboxanilides
WO2007110173A2 (en) * 2006-03-24 2007-10-04 Bayer Cropscience Ag Fungicidal active substance combinations
WO2007110173A3 (en) * 2006-03-24 2009-03-19 Bayer Cropscience Ag Fungicidal active substance combinations
JP2010517974A (en) * 2007-02-05 2010-05-27 ビーエーエスエフ ソシエタス・ヨーロピア Bactericidal mixture comprising substituted 1-methylpyrazol-4-ylcarboxyanilides
WO2008135480A2 (en) * 2007-05-02 2008-11-13 Basf Se Method for controlling specific fungal pathogen in soybeans by employing benodanil
WO2008135480A3 (en) * 2007-05-02 2009-09-24 Basf Se Method for controlling specific fungal pathogen in soybeans by employing benodanil
CN103907610A (en) * 2013-01-06 2014-07-09 江苏丰登农药有限公司 Sterilization composition containing fluxapyroxad and picoxystrobin, and application thereof
CN103907610B (en) * 2013-01-06 2016-05-04 江苏丰登作物保护股份有限公司 Bactericidal composition and the application thereof of a kind of fluorine-containing azoles bacterium acid amides and ZEN 90160

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