WO2010029030A2 - Fungicidal mixtures - Google Patents

Fungicidal mixtures Download PDF

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Publication number
WO2010029030A2
WO2010029030A2 PCT/EP2009/061513 EP2009061513W WO2010029030A2 WO 2010029030 A2 WO2010029030 A2 WO 2010029030A2 EP 2009061513 W EP2009061513 W EP 2009061513W WO 2010029030 A2 WO2010029030 A2 WO 2010029030A2
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WO
WIPO (PCT)
Prior art keywords
methyl
phenyl
carboxylic acid
pyrazole
difluoromethyl
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PCT/EP2009/061513
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French (fr)
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WO2010029030A3 (en
Inventor
Markus Gewehr
Jochen Dietz
Thomas Grote
Egon Haden
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Basf Se
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Publication of WO2010029030A2 publication Critical patent/WO2010029030A2/en
Publication of WO2010029030A3 publication Critical patent/WO2010029030A3/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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles

Definitions

  • the present invention relates to fungicidal mixtures comprising, as active components,
  • A) strobilurins dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxy- strobin, pyraclostrobin, pyribencarb, trifloxystrobin;
  • - carboxanilides benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fen- furam, fenhexamid, flutolanil, furametpyr, isotianil, kiralaxyl, mepronil, metalaxyl, meta- laxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penthiopyrad, tecloftalam, thif- luzamide, tiadinil, 3-dfluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid-(3',4',5'-tri- fluorobiphenyl-2-yl)-amide, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro- 1 H-pyrazole-4-
  • - triazoles azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusila- zole, flutriafol, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebu- conazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole; - imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizol;
  • - pyridines fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine;
  • - pyrimidines bupirimate, diflumetorim, fenarimol, ferimzone, mepanipyrim, nitrapyrin, nuarimol, pyrimethanil; - piperazines: triforine;
  • piperidines fenpropidin, 2- ⁇ 1-[2-(5-Methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-piperi- din-4-yl ⁇ -thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1-yl)-amide, 2- ⁇ 1 -[2-(5-Methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-piperidin-4-yl ⁇ -thiazole-4-carbo- xylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide;
  • non-aromatic 5-membered heterocycles famoxadone, fenamidone, octhilinone, pro- benazole; - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsul- fate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, tria- zoxide, tricyclazole, 2-butoxy-6-iodo-3-propylchromen-4-one, 5-ethyl-6-octyl-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-
  • guanidines guanidine, dodine, dodine free base, guazatine, guazatine-acetate, imi- noctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate); - antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, poly- oxine, validamycin A;
  • nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen;
  • fentin salts such as fentin-acetate, fentin chloride or fentin hydroxide
  • - sulfur-containing heterocyclyl compounds dithianon, isoprothiolane
  • organophosphorus compounds edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;
  • organochlorine compounds dichlofluanid, dichlorophen, flusulfamide, hexachloroben- zene, pencycuron, pentachlorphenole and its salts, phthalide, quintozene, thiophanate- methyl, tolylfluanid;
  • compound I refers to 2-[(2-fluoro-5-trifluoromethyl)phenyl- thio]-2-[3-(2-methoxyphenyl)-2-thiazolydinyliden]acetonitrile of formula I (common name: flutianil).
  • the invention relates to a method for controlling harmful fungi using the mixtures of the compound I and the compounds II, preferably to a method for controlling phytopathogenic harmful fungi, and to the use of the compound I and the compounds Il for preparing such mixtures, and also to compositions comprising such mixtures.
  • the present invention also comprises a method for protection of plant propagation material from harmful ungi comprising contacting the plant propagation materials with a mixture according to the invention in pesticidally effective amounts
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This in- eludes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • the term propagation material denotes seeds.
  • Cyanomethylene compounds inter alia the compound I (common name: flutianil), their preparation, compositions thereof and their action against harmful fungi are well known from the literature (EP-A 1 243 584, WO 08/13249).
  • the inventive mixtures can further contain one or more insecticides, fungicides, herbicides.
  • One embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from groups A) to F):
  • carboxamides - carboxanilides benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, fenfuram, fen- hexamid, isotianil, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penthiopyrad, tecloftalam, tiadinil, 3-dfluoromethyl-1-methyl-1 H-pyrazole- 4-carboxylic acid-(3',4',5'-trifluorobiphenyl-2-yl)-amide, N-(2-(1 ,3-dimethyl-butyl)-phe- nyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxylic acid amide, N-(2-bicyclopropyl-2-yl
  • carpropamid carpropamid, dicyclomet, mandiproamid, oxytetracyclin and silthiofarm;
  • azaconazole flusilazole, ipconazole, myclobutanil, oxpoconazole, pa- clobutrazole, penconazole, simeconazole, triticonazole, uniconazole;
  • - pyridines pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3- [5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine;
  • - pyrimidines bupirimate, diflumetorim, fenarimol, ferimzone, nitrapyrin, nuarimol;
  • non-aromatic 5-membered heterocycles octhilinone; - others: acibenzolar-S-methyl, amisulbrom, blasticidin-S, chinomethionat,, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, fenoxanil, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propyl- chromen-4-one, 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-pro- pyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, and 6-octyl-5-trifluoromethyl
  • guanidine guanidine, dodine, dodine free base, guazatine, guazatine-acetate;
  • - antibiotics kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, poly- oxine, validamycin A
  • - nitrophenyl derivates binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen
  • organometal compounds fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide
  • - sulfur-containing heterocyclyl compounds dithianon, isoprothiolane;
  • organophosphorus compounds edifenphos, iprobenfos, phosphorous acid and its salts;
  • organochlorine compounds dichlorophen, flusulfamide, hexachlorobenzene, penta- chlorphenole and its salts, phthalide, quintozene, tolylfluanid;
  • Another embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from dimoxystrobin, enestroburin, fluoxastrobin and orysastrobin.
  • a further embodiment relates to mixtures, comprising pyraclostrobin as component
  • a further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, car- propamid, dicyclomet, fenfuram, fenhexamid, flumorph, flumetover, fluopicolde, flu- opyram, isotianil, kiralaxyl, mandiproamid, metalaxyl, metalaxyl-M (mefenoxam), ofu- race, oxadixyl, oxycarboxin, oxytetracyclin, penthiopyrad, silthiofarm, tecloftalam, tiadi- nil, zoxamide, 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid-(3',4',5'-trifluoro- biphenyl-2-yl)-
  • a further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from bixafen, boscalid, penthiopyrad, 3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxylic acid-(3',4',5'-trifluorobiphenyl-2-yl)-amide, N-(2-(1 ,3-dimethyl- butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxylic acid amide, N-(2-bicyclo- propyl-2-yl-phenyl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide, N-(trans-2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carbox- ylic acid amide and N- ⁇ is ⁇ -bicyclopropyl ⁇ -y
  • a further embodiment relates to mixtures, comprising dimethomorph as component 2).
  • a further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from azaconazole, benomyl, carbendazim, cyazofamid, ethabox- am, etridiazole, fuberidazole, hymexazole, imazalil, ipconazole, myclobutanil, oxpocon- azole, paclobutrazole, penconazole, pefurazoate, prochloraz, prothioconazole, sime- conazole, thiabendazole, triflumizol, triticonazole, uniconazole and 2-(4-chloro-phenyl)- N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide.
  • compound Il selected from azaconazole, benomyl, carbendazim, cyazofamid, e
  • a further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from acibenzolar-S-methyl, amisulbrom, aldimorph, blasticidin-S, bupirimate, chinomethionat, debacarb, diclomezine, difenzoquat, difenzoquat-methyl- sulfate, diflumetorim, dodemorph, dodemorph-acetate, fenarimol, fenoxanil, ferimzone, nitrapyrin, nuarimol, octhilinone, oxolinic acid, piperalin, proquinazid, proxymidone, pyrifenox, triforine, pyroquilon, quinoxyfen, triazoxide, tricyclazole, vinclozolin,
  • a further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-propyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, and 6-octyl-5-trifluoromethyl- [1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine preferably.
  • 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5- a]pyrimidine-7-ylamine preferably.
  • a further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from ferbam, metam, methasulphocarb, metiram, propineb, propamocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester.
  • component 2 at least one compound Il selected from ferbam, metam, methasulphocarb, metiram, propineb, propamocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester.
  • a further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from basic copper sulfate, binapacryl, biphenyl, Bordeaux mixture, bronopol, copper acetate, copper hydroxide, copper oxychloride, cyflufenamid, cymoxanil, diphenylamin, dichlorophen, dinobuton, dinocap, dodine, dodine free base, edifenphos, fentin-acetate, fentin chloride, fentin hydroxide, fosetyl-aluminum, flusul- famide, guanidine, guazatine, guazatine-acetate, hexachlorobenzene, iminoctadine- triacetate, iminoctadine-tris(albesilate), iprobenfos, isoprothiolane, kasugamycin, kasu- gamycin hydrochloride-hydrate, mildi
  • a further embodiment relates to mixtures, comprising as component 2) at least one active compound Il selected from metrafenone and prohexadione-calcium.
  • a further embodiment relates to mixtures, comprising dithianon as component 2).
  • compositions described comprise the active substances in synergistically effective amounts.
  • Table B Mixtures comprising compound I (flutianil) and one compound II, wherein the compound Il corresponds in each case to one line of the table:
  • the mixtures comprising the components 1) and 2) and the compositions thereof, respectively, or the simultaneous, that is joint or separate, use of a component 1 ) and a component 2) are distinguished by excellent activity against a broad spectrum of phy- topathogenic phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomyce- tes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromy- cetes (syn. Fungi imperfecti).
  • Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the mixtures according to the invention and the compositions thereof, respectively, are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • cereals e. g. wheat, rye, barley, triticale, oats or rice
  • beet e. g. sugar beet or fodder beet
  • fruits such as pomes, stone fruits or soft fruits, e. g.
  • mixtures according to the invention and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • field crops such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • treatment of plant propagation materials with mixtures according to the invention and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • cultiva plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://www.bio.org/speeches/pubs/er/agrLproducts.asp).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not Nm- ited to targeted post-transtional modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • HPPD hydroxyphenylpyruvate dioxygenase
  • ALS acetolactate synthase
  • sulfonyl ureas see e. g.
  • plants are also covered that are by the use of recombinant DNA tech- niques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ - endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, Vl P3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • VIP1 , VIP2, Vl P3 or VIP3A vegetative insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomy- cetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of sodium
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g.
  • plants that produce health- promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada). Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • a modified amount of substances of content or new substances of content specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • the mixtures according to the invention and compositions thereof, repectively, are particularly suitable for controlling the following plant diseases: Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat; Aphano- myces spp. on sugar beets and vegetables; Ascochyta spp.
  • Albugo spp. white rust
  • vegetables e. g. A. Candida
  • sunflowers e. g. A. tragopogonis
  • Alternaria spp. Alternaria leaf spot
  • rape A.
  • Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad- leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e.g.
  • Gray leaf spot C. zeae-maydis
  • rice sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice
  • Cladosporium spp. on tomatoes e. g. C. fulvum: leaf mold
  • cereals e. g. C. herbarum (black ear) on wheat
  • Cochliobolus anamorph: Helminthosporium of Bipolaris
  • spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C.
  • sa- sakii sheath blight
  • Corynespora cassiicola leaf spots
  • Cycloconium spp. e. g. C. oleaginum on olive trees
  • Cylindrocarpon spp. e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.
  • liriodendri Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. D.
  • tritici-repentis tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeo- acremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E.
  • ampelina anthracnose
  • Entyloma oryzae leaf smut
  • Epicoccum spp. black mold
  • Erysiphe spp. potowdery mildew
  • sugar beets E. betae
  • vegetables e. g. E. pisi
  • cucurbits e. g. E. cichoracearum
  • cabbages e. g. E. cruciferarum
  • Eutypa lata Eutypa canker or dieback, anamorph: Cytosporina lata, syn.
  • Drechslera, teleomorph Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; lsariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M.
  • stem rot P. phaseoli, teleomorph: Diaporthe phaseolorum
  • Physoderma maydis brown spots
  • Phytophthora spp. wilt, root, leaf, fruit and stem root
  • paprika and cucurbits e. g. P. capsici
  • soybeans e. g. P. megasperma, syn. P. sojae
  • potatoes and tomatoes e. g. P. infestans: late blight
  • broad-leaved trees e. g. P.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew on rosa- ceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples
  • Polymyxa spp. e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P.
  • Pseudocercosporella herpotrichoides eyespot, teleomorph: Tapesia yallundae
  • Pseudoperonospora downy mildew
  • Pseudopezicula tracheiphila red fire disease or .rotbrenner', anamorph: Phialophora
  • Puccinia spp. rusts on various plants, e. g. P. triticina (brown or leaf rust), P.
  • striiformis stripe or yellow rust
  • P. hordei dwarf rust
  • P. graminis seed or black rust
  • P. recondita brown or leaf rust
  • cereals such as e. g. wheat, barley or rye, and asparagus (e. g. P. asparagi); Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P.
  • grisea on turf and cereals Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphani- dermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R.
  • S. rolfsii or S. scle- rotiorum Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagono- spora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn.
  • Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn.
  • Taphrina spp. e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums
  • Thielaviopsis spp. black root rot
  • controversa dwarf bunt
  • Typhula incarnata grey snow mold
  • Uro- cystis spp. e. g. U. occulta (stem smut) on rye
  • Uromyces spp. rust
  • vegetables such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae)
  • Ustilago spp. loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp.
  • mixtures according to the invention and compositions thereof, resepctively, are also suitable for controlling harmful fungi in the protection of materials (e. g. wood, pa- per, paint dispersions, fiber or fabrics) and in the protection of stored products.
  • materials e. g. wood, pa- per, paint dispersions, fiber or fabrics
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Candida spp. and Saccharomyces cerevisae are noteworthy of note: Candida spp. and Saccharomyces cerevisae.
  • the mixtures according to the invention and compositions thereof, resepectively, may be used for improving the health of a plant.
  • the invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of mixtures according to the invention and compositions thereof, respectively.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e. g. improved plant growth and/or greener leaves ("greening effect")
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e. g. improved content or composition of certain ingredients
  • the compound I and compounds Il or the mixtures according to the invention are employed as such or in form of compositions by treating the fungi, their habitat or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Compound I and compounds Il can be applied simultaneously jointly, simultaneously separately or in succession.
  • Plant propagation materials may be treated with mixtures according to the invention as such or a composition thereof prophylactically either at or before planting or trans- planting.
  • the invention also relates to agrochemical compositions comprising a solvent or solid carrier and a mixture according to the invention and to the use for controlling harmful fungi.
  • the invention also relates to the use of the compound I and at least one compound Il for preparing a composition suitable for controlling harmful fungi.
  • An agrochemical composition comprises a fungicidally effective amount of a mixture according to the invention.
  • the term "effective amount” denotes an amount of the composition or of the mixtures according to the invention, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific mixture used.
  • the compound I and the compounds II, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • agrochemical compositions e. g. solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the composition type depends on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.
  • composition types are suspensions (SC, OD, FS), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), which can be water-soluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF).
  • composition types e. g. SC, OD, FS, WG, SG, WP, SP, SS, WS, GF
  • composition types such as DP, DS, GR, FG, GG and MG are usually used undiluted.
  • compositions are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J.
  • the agrochemical compositions may also comprise auxiliaries which are customary in agrochemical compositions.
  • the auxiliaries used depend on the particular applica- tion form and active substance, respectively.
  • auxiliaries are solvents, solid carriers, dispersants or emulsi- fiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment for- mulations).
  • Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e. g.
  • Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and prod- ucts of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse ® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet ® types, Akzo Nobel, U.S.A.), dibutylnaphthalene- sulfonic acid (Nekal ® types, BASF, Germany), and fatty acids, alkylsulfonates, alkyl- arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers,
  • aromatic sulfonic acids such as ligninsoulfonic acid (Borresperse
  • methylcellulose g. methylcellulose
  • hydrophobically modified starches polyvinyl alcohols (Mowiol ® types, Clariant, Switzerland), polycarboxylates (Sokolan ® types, BASF, Germany), polyalkoxylates, polyvinyl- amines (Lupasol ® types, BASF, Germany), polyvinylpyrrolidone and the copolymers therof.
  • thickeners i. e. compounds that impart a modified flowability to compositions, i. e. high viscosity under static conditions and low viscosity during agitation
  • thickeners are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan ® , CP Kelco, U.S.A.), Rhodopol ® 23 (Rhodia, France), Veegum ® (RT. Vanderbilt, U.S.A.) or Attaclay ® (Engelhard Corp., NJ, USA).
  • Bactericides may be added for preservation and stabilization of the composition.
  • suitable bactericides are those based on dichlorophene and benzyl- alcohol hemi formal (Proxel ® from ICI or Acticide ® RS from Thor Chemie and Kathon ® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide ® MBS from Thor Chemie).
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • anti-foaming agents examples include silicone emulsions (such as e. g. Silikon ® SRE, Wacker, Germany or Rhodorsil ® , Rhodia, France), long chain alcohols, fatty ac- ids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.
  • Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples to be mentioned und the designations rhodamin B, C. I. pigment red 1 12, C. I. solvent red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • tackifiers or binders examples include polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose ® , Shin-Etsu, Japan).
  • Powders, materials for spreading and dusts can be prepared by mixing or conco- mitantly grinding the compounds I and Il and, if appropriate, further active substances, with at least one solid carrier.
  • Granules e. g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers.
  • solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.
  • ammonium sulfate ammonium phosphate, ammonium nitrate, ureas
  • products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • composition types are:
  • composition types for dilution with water i) Water-soluble concentrates (SL, LS)
  • a composition having a content of 10% by weight of active substance is obtained.
  • Dispersible concentrates (DC) 20 parts by weight of a compound I according to the invention are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e. g. polyvinylpyrrolidone. Dilution with water gives a dispersion.
  • the active substance content is 20% by weight.
  • Emulsifiable concentrates 15 parts by weight of a compound I 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 with water gives an emulsion. The composition has an active substance content of 15% by weight.
  • Emulsions EW, EO, ES 25 parts by weight of a compound I according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • a compound I according to the invention 50 parts by weight of a compound I according to the invention are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as wa- ter-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solu- tion of the active substance.
  • the composition has an active substance content of 50% by weight. vii) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
  • a compound I according to the invention 20 parts by weight of a compound I according to the invention are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained.
  • a compound I according to the invention 5 parts by weight of a compound I according to the invention are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight.
  • Granules (GR, FG, GG, MG) 0.5 parts by weight of a compound I according to the invention is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray- drying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5% by weight.
  • Xi)ULV solutions 10 parts by weight of a compound I according to the invention are dissolved in 90 parts by weight of an organic solvent, e. g. xylene. This gives a composition to be applied undiluted having an active substance content of 10% by weight.
  • the agrochemical compositions generally comprise between 0.01 and 95%, pref- erably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substances.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Water-soluble concentrates (LS), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES) emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted.
  • compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.
  • Application can be carried out before or during sowing.
  • Methods for applying or treating agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • the compounds or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • a suspension-type (FS) composition is used for seed treatment.
  • a FS composition may comprise 1-800 g/l of active substances, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • the mixtures according to the invention can be used as such or in the form of their compositions, e. g.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil and such concentrates are suitable for dilution with water.
  • the active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1 % by weight of active substance.
  • the active substances may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • the invention In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
  • plant propagation materials preferably seeds, comprising the mixture according to the invention or a composition thereof in an amout as used for treatment thereof.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are, e. g., 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substances or the compositions com- prising them, if appropriate not until immediately prior to use (tank mix).
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240 ® ; alcohol alkoxylates such as Atplus 245 ® , Atplus MBA 1303 ® , Plurafac LF 300 ® and Lutensol ON 30 ® ; EO/PO block polymers, e. g. Pluronic RPE 2035 ® and Genapol B ® ; alcohol ethoxylates such as Lutensol XP 80 ® ; and dioctyl sul- fosuccinate sodium such as Leophen RA ® .
  • organic modified polysiloxanes such as Break Thru S 240 ®
  • alcohol alkoxylates such as Atplus 245 ® , Atplus MBA 1303 ® , Plurafac LF 300 ® and Lutensol ON 30 ®
  • EO/PO block polymers e. g. Pluronic RPE 2035 ® and Genapol B ®
  • applying compound I together with at least one compound Il together is to be understood to denote, that compound I and at least one com- pound Il occur simultaneously at the site of action (i.e. the harmful fungi to be controlled or their habitats such as infected plants, plant propagation materials, particularly seeds, surfaces, materials or the soil as well as plants, plant propagation materials, particularly seeds, soil, surfaces, materials or rooms to be protected from fungal attack) in a fungicidally effective amount.
  • This can be obtained by applying the compound I and at least one compound Il simultaneously, that is jointly (e. g.
  • tank-mix or sper- ately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s).
  • the order of application is not essential for working of the present invention.
  • the weight ratio of component 1 and component 2 generally depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :3 to 3:1.
  • the weight ratio of component 1 and component 2 may also be in the range of from 1000:1 to 1 :10, preferably in the range of from 1000:1 to 1 :1 , more preferably in the range of from 1000:1 to 20:1 in particular in the range of from 1000:1 to 100:1.
  • compositions according to the invention can be used indi- vidually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts.
  • kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition.
  • kits may include one or more fungicide component(s) and/or an adjuvant component and/or a insecticide component and/or a growth regulator component and/or a her- bicde.
  • One or more of the components may already be combined together or pre- formulated.
  • the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister.
  • two or more components of a kit may be packaged separately, i. e., not pre- formulated.
  • kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition.
  • a component of the kit may be applied separately from or together with the further components or as a component of a combination composition according to the invention for preparing the composition according to the invention.
  • the user applies the composition according to the invention usually from a predos- age device, a knapsack sprayer, a spray tank or a spray plane.
  • the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 50 to 500 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area, preferably 100 to 400 liters.
  • individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).
  • either individual components of the composition according to the invention or partially premixed components may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate (tank mix).
  • compositions according to the invention can be applied jointly (e. .g. after tankmix) or consecutively.
  • the compositions according to the invention can, in the use form as fungicides, also be present together with other active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix).
  • compositions comprising component 1 ) and 2), wherein component 2) consists of only one compound II, are employed.
  • component 2) consists of two or, if appropriate, more compounds Il may be advantageous.
  • Suitable further active components in the above sense are in particular the active compounds Il mentioned at the outset, and in particular the preferred compounds Il mentioned above.
  • ternary mixtures comprising, in addition to component 1) and component 2) consisting of one active compound Il mentioned above, a further active compound V selected from active compound groups G) to P):
  • active substances in conjunction with which the compounds according to the invention can be used, is intended to illustrate the possible combinations but does not limit them: G) strobilurins azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, meto- minostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin, 2-(2-(6-(3-chloro-2-methyl-phenoxy)-5-fluoro-pyrimidin-4-yloxy)-phenyl)-2-methoxy- imino-N-methyl-acetamide, 3-methoxy-2-(2-(N-(4-methoxy-phenyl)-cyclopropane
  • - carboxanilides benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fen- furam, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penthiopyrad, tecloftalam, thifluzamide, tiadinil, 2-amino-4-methyl-thiazole-5-carboxanilide,
  • - carboxylic morpholides dimethomorph, flumorph
  • - benzoic acid amides flumetover, fluopicolde, fluopyram, zoxamide, N-(3-Ethyl- 3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide;
  • carpropamid carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthio- farm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide;
  • azoles - triazoles azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusi- lazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobu- tanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1 ,2,4]triazol-1-yl)-cycloheptanol
  • - pyridines fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine,
  • dicarboximides fluoroimid, iprodione, procymidone, vinclozolin;
  • non-aromatic 5-membered heterocycles famoxadone, fenamidone, flutianil, octhili- none, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro-pyrazole- 1-carbothioic acid S-allyl ester; - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methyl- sulfate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quin- oxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propyl
  • - antibiotics kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, poly- oxine, validamycin A
  • - nitrophenyl derivates binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen
  • organometal compounds fentin salts, such as fentin-acetate, fentin chloride or fen- tin hydroxide;
  • organophosphorus compounds edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;
  • organochlorine compounds chlorothalonil, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quinto- zene, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide; - inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
  • N) growth regulators abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dike- gulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate,
  • acetochlor alachlor, butachlor, dimethachlor, dimethenamid, flufena- cet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
  • - aryloxyphenoxypropionates clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, ha- loxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl; - Bipyridyls: diquat, paraquat;
  • - (thio)carbamates asulam, butylate, carbetamide, desmedipham, dimepiperate, ep- tam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyribu- ticarb, thiobencarb, triallate;
  • - diphenyl ethers acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lac- tofen, oxyfluorfen; - hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil; imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, ima- zethapyr;
  • - phenoxy acetic acids clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
  • - pyrazines chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
  • - pyridines aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, pi- cloram, picolinafen, thiazopyr;
  • - sulfonyl ureas amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlor- sulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfu- ron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, meso- sulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-
  • ureas chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
  • acetolactate synthase inhibitors bispyribac-sodium, cloransulam-methyl, di- closulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, pe- noxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyrimi- nobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
  • organo(thio)phosphates acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, me- thidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, pa- raoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, pho- xim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbu- fos, triazophos, trichlorfon;
  • - carbamates alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;
  • pyrethroids allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfen- valerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin,
  • - nicotinic receptor agonists/antagonists compounds clothianidin, dinotefuran, imida- cloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chloro-thiazol-5- ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane;
  • GABA antagonist compounds endosulfan, ethiprole, fipronil, vaniliprole, pyraflupro- Ie, pyriprole, 5-amino-1-(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1 H-pyrazole-3- carbothioic acid amide;
  • macrocyclic lactone insecticides abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram
  • - mitochondrial electron transport inhibitor I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim; - METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;
  • - oxidative phosphorylation inhibitors cyhexatin, diafenthiuron, fenbutatin oxide, propargite; moulting disruptor compounds: cryomazine; - mixed function oxidase inhibitors: piperonyl butoxide;
  • the present invention furthermore relates to agrochemical compositions comprising a mixture of compound I (component 1 ) and at least one compound Il (component 2) and at least one further active substance V useful for plant protection, e. g. selected from the groups G) to P) (component 3), in particular one further fungicide, e. g. one or more fungicide from the groups G) to M), as described above, and if desired one suitable solvent or solid carrier.
  • agrochemical compositions comprising a mixture of compound I (component 1 ) and at least one compound Il (component 2) and at least one further active substance V useful for plant protection, e. g. selected from the groups G) to P) (component 3), in particular one further fungicide, e. g. one or more fungicide from the groups G) to M), as described above, and if desired one suitable solvent or solid carrier.
  • fungicide e. g. one or more fungicide from the groups G) to M
  • combating harmful fungi with a mixture of compound I and at least one compound Il and at least one fungicide from groups G) to M), as described above, is more efficient than combating those fungi with a mixture of compound I and at least one compound Il or individual fungicides from groups G) to M) (synergistic mixtures).
  • the weight ratio of component 1 and component 2 depends from the properties of the active substances used, preferably it is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1 , and the weight ratio of component 1 and component s preferably is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1.
  • the active compounds V mentioned above, their preparation and their action against harmful fungi, insects or weeds are generally known (cf., for example, http://www.hclrss.demon.co.uk/index.html); they are commercially available.
  • the compounds described by IUPAC nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031 ; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ;
  • an active compound selected from the group of the other fungicides M) selected from the group consisting of dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, chlorothalonil, dichlofluanid, thiophanate
  • the active compounds were formulated separately as a stock solution of a concentration of 10 000 ppm in DMSO.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Phytophtora infestans containing a pea juice-based aqueous nutrient medium was then added.
  • the plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
  • the measured parameters were compared to the growth of the active compound- free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies.
  • An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing.
  • test results show that, by virtue of the synergism, the mixtures according to the invention are considerabley more effective than had been predicted using Colby's for- mula, different from mixtures known in the art used in the comparative trial.

Abstract

The present invention relates to fungicidal mixtures comprising, as active components, the fungicidal compound I and at least one further active compound as defined in the claims in synergistically effective amounts, and to a method for controlling harmful fungi using the mixtures of the compound I and the compounds II, and to the use of the compound I and the compounds Il for preparing such mixtures, and also to compositions comprising such mixtures.

Description

Fungicidal mixtures
Description
The present invention relates to fungicidal mixtures comprising, as active components,
1 ) 2-[(2-fluoro-5-trifluoromethyl)phenylthio]-2-[3-(2-methoxyphenyl)-2-thiazolydinyl- iden]acetonitrile I
Figure imgf000002_0001
and
2) at least one active compound Il selected from groups A) to F):
A) strobilurins: dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxy- strobin, pyraclostrobin, pyribencarb, trifloxystrobin;
B) carboxamides:
- carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fen- furam, fenhexamid, flutolanil, furametpyr, isotianil, kiralaxyl, mepronil, metalaxyl, meta- laxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penthiopyrad, tecloftalam, thif- luzamide, tiadinil, 3-dfluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid-(3',4',5'-tri- fluorobiphenyl-2-yl)-amide, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro- 1 H-pyrazole-4-carboxylic acid amide, N-(2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl- 1-methyl-1 H-pyrazole-4-carboxylic acid amide, N-(trans-2-bicyclopropyl-2-yl-phenyl)- 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide, N-(cis-2-bicyclopropyl- 2-yl-phenyl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide;
- carboxylic morpholides: dimethomorph, flumorph;
- benzoic acid amides: flumetover, fluopicolde, fluopyram, zoxamide;
- other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracyclin and silthiofarm;
C) azoles:
- triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusila- zole, flutriafol, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebu- conazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole; - imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizol;
- benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;
- others: ethaboxam, etridiazole, hymexazole and 2-(4-chloro-phenyl)-N-[4-(3,4-dimeth- oxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide; D) heterocyclic compounds:
- pyridines: fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine;
- pyrimidines: bupirimate, diflumetorim, fenarimol, ferimzone, mepanipyrim, nitrapyrin, nuarimol, pyrimethanil; - piperazines: triforine;
- pyrroles: fenpiclonil, fludioxonil;
- morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph;
- piperidines: fenpropidin, 2-{1-[2-(5-Methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-piperi- din-4-yl}-thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1-yl)-amide, 2-{1 -[2-(5-Methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-thiazole-4-carbo- xylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide;
- dicarboximides: fluoroimid, iprodione, proxymidone, vinclozolin;
- non-aromatic 5-membered heterocycles: famoxadone, fenamidone, octhilinone, pro- benazole; - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsul- fate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, tria- zoxide, tricyclazole, 2-butoxy-6-iodo-3-propylchromen-4-one, 5-ethyl-6-octyl-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-propyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-yl- amine, and 6-octyl-5-trifluoromethyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine;
E) carbamates:
- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram;
- carbamates: benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl)-carba- mic acid-(4-fluorophenyl) ester;
F) other active substances:
- guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, imi- noctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate); - antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, poly- oxine, validamycin A;
- nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen;
- organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; - sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane;
- organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; - organochlorine compounds: dichlofluanid, dichlorophen, flusulfamide, hexachloroben- zene, pencycuron, pentachlorphenole and its salts, phthalide, quintozene, thiophanate- methyl, tolylfluanid;
- inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamin, metrafenone, mil- diomycin, oxin-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N'-(4-(4-chloro- 3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl forma- midine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine and N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)- phenyl)-N-ethyl-N-methyl formamidine; in a synergistically effective amounts.
The above-referred mixtures are hereinbelow also referred as "mixtures according to the invention". The term "compound I" refers to 2-[(2-fluoro-5-trifluoromethyl)phenyl- thio]-2-[3-(2-methoxyphenyl)-2-thiazolydinyliden]acetonitrile of formula I (common name: flutianil).
Moreover, the invention relates to a method for controlling harmful fungi using the mixtures of the compound I and the compounds II, preferably to a method for controlling phytopathogenic harmful fungi, and to the use of the compound I and the compounds Il for preparing such mixtures, and also to compositions comprising such mixtures.
Additionally, the present invention also comprises a method for protection of plant propagation material from harmful ungi comprising contacting the plant propagation materials with a mixture according to the invention in pesticidally effective amounts
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This in- eludes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring. In a particular preferred embodiment, the term propagation material denotes seeds. Cyanomethylene compounds, inter alia the compound I (common name: flutianil), their preparation, compositions thereof and their action against harmful fungi are well known from the literature (EP-A 1 243 584, WO 08/13249).
Mixtures of the compound I with chlorothalonil, azoxystrobin and hexaconazol have been described earlier (WO 04/43149). In addition, WO 04/43149 generally mentions mixtures of certain fungicide classes with cyanomethylene compounds. Furthermore, mixtures of various fungicides, inter alia compound I, with cyprodinil and isopyrazam, respectively, have been mentioned earlier (WO 07/06355, WO 07/115766). The compounds Il referred to as component 2, their preparation and their activity against harmful fungi are generally known (cf.: http://www.alanwood.net/pesticides/). For instance, the commercially available compounds may be found in The Pesticide Manual, 13th Edition, British Crop Protection Council (2003) among other publications. The compounds described by IUPAC nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031 ; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624).
The fungicidal activity and in particular the persistence and spectrum of activity of compound I and its mixtures often leaves something to be desired.
It is an object of the present invention, with a view to reducing the application rates and broadening the activity spectrum of the known compounds, to provide mixtures which, at a reduced total amount of active compounds applied, have improved activity, in particular persistence, against harmful fungi.
We found that this object is achieved by the mixtures defined as the outset. Moreover, we have found that applying the compound I and compounds Il simultaneously, either together or speerately, or applying the compound I and compounds Il in succession provides better control of harmful fungi than is possible with the individual compounds (synergistic mixtures).
The inventive mixtures can further contain one or more insecticides, fungicides, herbicides. One embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from groups A) to F):
A) strobilurins dimoxystrobin, enestroburin, fluoxastrobin, orysastrobin, picoxystrobin, pyribencarb;
B) carboxamides - carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, fenfuram, fen- hexamid, isotianil, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penthiopyrad, tecloftalam, tiadinil, 3-dfluoromethyl-1-methyl-1 H-pyrazole- 4-carboxylic acid-(3',4',5'-trifluorobiphenyl-2-yl)-amide, N-(2-(1 ,3-dimethyl-butyl)-phe- nyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxylic acid amide, N-(2-bicyclopropyl-2-yl- phenyl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide, N-(trans-2-bi- cyclopropyl-2-yl-phenyl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide, N-(cis-2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carbo- xylic acid amide;
- carboxylic morpholides: flumorph;
- benzoic acid amides: flumetover, fluopicolde, fluopyram, zoxamide;
- other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracyclin and silthiofarm;
C) azoles
- triazoles: azaconazole, flusilazole, ipconazole, myclobutanil, oxpoconazole, pa- clobutrazole, penconazole, simeconazole, triticonazole, uniconazole;
- imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; - benzimidazoles: fuberidazole;
- others: ethaboxam, etridiazole, hymexazole and 2-(4-chloro-phenyl)-N-[4-(3,4-dimeth- oxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
D) heterocyclic compounds
- pyridines: pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3- [5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine;
- pyrimidines: bupirimate, diflumetorim, fenarimol, ferimzone, nitrapyrin, nuarimol;
- piperazines: triforine;
- morpholines: aldimorph, dodemorph, dodemorph-acetate;
- piperidines: 2-{1 -[2-(5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}- thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1-yl)-amide,
2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4-car- boxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide;
- dicarboximides: vinclozolin;
- non-aromatic 5-membered heterocycles: octhilinone; - others: acibenzolar-S-methyl, amisulbrom, blasticidin-S, chinomethionat,, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, fenoxanil, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propyl- chromen-4-one, 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-pro- pyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, and 6-octyl-5-trifluoromethyl-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine-7-ylamine;
E) carbamates
- thio- and dithiocarbamates: ferbam, metam, methasulphocarb, metiram, propineb, ziram;
- carbamates: propamocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4- cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
F) other active substances
- guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate;
- antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, poly- oxine, validamycin A; - nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; - sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane;
- organophosphorus compounds: edifenphos, iprobenfos, phosphorous acid and its salts;
- organochlorine compounds: dichlorophen, flusulfamide, hexachlorobenzene, penta- chlorphenole and its salts, phthalide, quintozene, tolylfluanid;
- inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamin, metrafenone, mildiomycin, oxin-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N'-(4-(4- chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine and N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)- phenyl)-N-ethyl-N-methyl formamidine; in a synergistically effective amounts. Another embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from dimoxystrobin, enestroburin, fluoxastrobin and orysastrobin. A further embodiment relates to mixtures, comprising pyraclostrobin as component
2).
A further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, car- propamid, dicyclomet, fenfuram, fenhexamid, flumorph, flumetover, fluopicolde, flu- opyram, isotianil, kiralaxyl, mandiproamid, metalaxyl, metalaxyl-M (mefenoxam), ofu- race, oxadixyl, oxycarboxin, oxytetracyclin, penthiopyrad, silthiofarm, tecloftalam, tiadi- nil, zoxamide, 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid-(3',4',5'-trifluoro- biphenyl-2-yl)-amide, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyraz- ole-4-carboxylic acid amide, N-(2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxylic acid amide, N-(trans-2-bicyclopropyl-2-yl-phenyl)-3-difluoro- methyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide, and N-(cis-2-bicyclopropyl-2-yl- phenyl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide. A further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from bixafen, boscalid, penthiopyrad, 3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxylic acid-(3',4',5'-trifluorobiphenyl-2-yl)-amide, N-(2-(1 ,3-dimethyl- butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxylic acid amide, N-(2-bicyclo- propyl-2-yl-phenyl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide, N-(trans-2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carbox- ylic acid amide and N-^is^-bicyclopropyl^-yl-pheny^-S-difluoromethyl-i-methyl- 1 H-pyrazole-4-carboxylic acid amide, in particular 3-difluoromethyl-1 -methyl-1 H-pyra- zole-4-carboxylic acid-(3',4',5'-trifluorobiphenyl-2-yl)-amide.
A further embodiment relates to mixtures, comprising dimethomorph as component 2).
A further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from azaconazole, benomyl, carbendazim, cyazofamid, ethabox- am, etridiazole, fuberidazole, hymexazole, imazalil, ipconazole, myclobutanil, oxpocon- azole, paclobutrazole, penconazole, pefurazoate, prochloraz, prothioconazole, sime- conazole, thiabendazole, triflumizol, triticonazole, uniconazole and 2-(4-chloro-phenyl)- N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide. A further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from acibenzolar-S-methyl, amisulbrom, aldimorph, blasticidin-S, bupirimate, chinomethionat, debacarb, diclomezine, difenzoquat, difenzoquat-methyl- sulfate, diflumetorim, dodemorph, dodemorph-acetate, fenarimol, fenoxanil, ferimzone, nitrapyrin, nuarimol, octhilinone, oxolinic acid, piperalin, proquinazid, proxymidone, pyrifenox, triforine, pyroquilon, quinoxyfen, triazoxide, tricyclazole, vinclozolin,
3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3-[5-(4-methyl-phenyl)- 2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazol- 1-yl)-acetyl]-piperidin-4-yl}-thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naph- thalen-1 -yl)-amide, 2-{1 -[2-(5-methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-piperidin- 4-yl}-thiazole-4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1 -yl-amide and 2-butoxy-6-iodo-3-propylchromen-4-one.
A further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-propyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, and 6-octyl-5-trifluoromethyl- [1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine preferably. 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5- a]pyrimidine-7-ylamine.
A further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from ferbam, metam, methasulphocarb, metiram, propineb, propamocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester.
A further embodiment relates to mixtures, comprising as component 2) at least one compound Il selected from basic copper sulfate, binapacryl, biphenyl, Bordeaux mixture, bronopol, copper acetate, copper hydroxide, copper oxychloride, cyflufenamid, cymoxanil, diphenylamin, dichlorophen, dinobuton, dinocap, dodine, dodine free base, edifenphos, fentin-acetate, fentin chloride, fentin hydroxide, fosetyl-aluminum, flusul- famide, guanidine, guazatine, guazatine-acetate, hexachlorobenzene, iminoctadine- triacetate, iminoctadine-tris(albesilate), iprobenfos, isoprothiolane, kasugamycin, kasu- gamycin hydrochloride-hydrate, mildiomycin, nitrthal-isopropyl, oxin-copper, streptomycin, oxin-copper, phosphorous acid and its salts, polyoxine, phthalide, quintozene, spi- roxamine, sulfur, tecnazen, tolclofos-methyl, tolylfluanid, validamycin A, N'-(4-(4-chloro- 3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine and N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)- phenyl)-N-ethyl-N-methyl formamidine.
A further embodiment relates to mixtures, comprising as component 2) at least one active compound Il selected from metrafenone and prohexadione-calcium. A further embodiment relates to mixtures, comprising dithianon as component 2).
With respect to their intended use, the following mixtures of the compound I and one compound Il listed in the table B below are more preferred. Preferably, the compositions described comprise the active substances in synergistically effective amounts.
Table B: Mixtures comprising compound I (flutianil) and one compound II, wherein the compound Il corresponds in each case to one line of the table:
Figure imgf000009_0001
Figure imgf000009_0002
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000011_0002
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000012_0002
The mixtures comprising the components 1) and 2) and the compositions thereof, respectively, or the simultaneous, that is joint or separate, use of a component 1 ) and a component 2), are distinguished by excellent activity against a broad spectrum of phy- topathogenic phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomyce- tes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromy- cetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
The mixtures according to the invention and the compositions thereof, respectively, are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
Preferably, mixtures according to the invention and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
Preferably, treatment of plant propagation materials with mixtures according to the invention and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://www.bio.org/speeches/pubs/er/agrLproducts.asp). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not Nm- ited to targeted post-transtional modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imida- zolinones (see e. g. US 6,222,100, WO 01/82685, WO 00/026390, WO 97/41218, WO 98/002526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/014357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate syn- thase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e.g. EP-A 242 236, EP-A 242 246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering.
Furthermore, plants are also covered that are by the use of recombinant DNA tech- niques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ- endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, Vl P3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhab- dus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomy- cetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants. Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health- promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada). Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany).
The mixtures according to the invention and compositions thereof, repectively, are particularly suitable for controlling the following plant diseases: Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat; Aphano- myces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e.g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad- leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e.g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miy- abeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (an- thracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sa- sakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeo- acremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium (teleomorph: Gib- berella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxy- sporum on tomatoes, F. solani on soybeans and F. verticillioides on corn; Gaeumanno- myces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grain- staining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; lsariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad-leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosa- ceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or .rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, and asparagus (e. g. P. asparagi); Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphani- dermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium se- calis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. scle- rotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagono- spora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Uro- cystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
The mixtures according to the invention and compositions thereof, resepctively, are also suitable for controlling harmful fungi in the protection of materials (e. g. wood, pa- per, paint dispersions, fiber or fabrics) and in the protection of stored products. As to the protection of wood and construction materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyro- myces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
The mixtures according to the invention and compositions thereof, resepectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of mixtures according to the invention and compositions thereof, respectively.
The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.The above identified indicators for the health condition of a plant may be interdependent or may result from each other. The compound I and compounds Il or the mixtures according to the invention are employed as such or in form of compositions by treating the fungi, their habitat or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi. Compound I and compounds Il can be applied simultaneously jointly, simultaneously separately or in succession.
Plant propagation materials may be treated with mixtures according to the invention as such or a composition thereof prophylactically either at or before planting or trans- planting.
The invention also relates to agrochemical compositions comprising a solvent or solid carrier and a mixture according to the invention and to the use for controlling harmful fungi.
The invention also relates to the use of the compound I and at least one compound Il for preparing a composition suitable for controlling harmful fungi.
An agrochemical composition comprises a fungicidally effective amount of a mixture according to the invention. The term "effective amount" denotes an amount of the composition or of the mixtures according to the invention, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific mixture used.
The compound I and the compounds II, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The composition type depends on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.
Examples for composition types are suspensions (SC, OD, FS), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), which can be water-soluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF).
Usually the composition types (e. g. SC, OD, FS, WG, SG, WP, SP, SS, WS, GF) are employed diluted. Composition types such as DP, DS, GR, FG, GG and MG are usually used undiluted.
The compositions are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, New York, 1961), Hance et al.: Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation technology (Wiley VCH Verlag, Weinheim, 2001 ).
The agrochemical compositions may also comprise auxiliaries which are customary in agrochemical compositions. The auxiliaries used depend on the particular applica- tion form and active substance, respectively.
Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsi- fiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment for- mulations).
Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their de- rivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as cyclohexanone and gamma-butyrolactone, fatty acid dimethyla- mides, fatty acids and fatty acid esters and strongly polar solvents, e. g. amines such as N-methylpyrrolidone.
Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and prod- ucts of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Suitable surfactants (adjuvants, wtters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene- sulfonic acid (Nekal® types, BASF, Germany), and fatty acids, alkylsulfonates, alkyl- arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearyl- phenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and proteins, denatured proteins, polysaccharides (e. g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols (Mowiol® types, Clariant, Switzerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvinyl- amines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers therof.
Examples for thickeners (i. e. compounds that impart a modified flowability to compositions, i. e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (RT. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA).
Bactericides may be added for preservation and stabilization of the composition. Examples for suitable bactericides are those based on dichlorophene and benzyl- alcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie).
Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Examples for anti-foaming agents are silicone emulsions (such as e. g. Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty ac- ids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.
Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples to be mentioned und the designations rhodamin B, C. I. pigment red 1 12, C. I. solvent red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples for tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).
Powders, materials for spreading and dusts can be prepared by mixing or conco- mitantly grinding the compounds I and Il and, if appropriate, further active substances, with at least one solid carrier.
Granules, e. g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Examples for composition types are:
1. Composition types for dilution with water i) Water-soluble concentrates (SL, LS)
10 parts by weight of a compound I according to the invention are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a composition having a content of 10% by weight of active substance is obtained. ii) Dispersible concentrates (DC) 20 parts by weight of a compound I according to the invention are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e. g. polyvinylpyrrolidone. Dilution with water gives a dispersion. The active substance content is 20% by weight. iii) Emulsifiable concentrates (EC) 15 parts by weight of a compound I 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 with water gives an emulsion. The composition has an active substance content of 15% by weight. iv)Emulsions (EW, EO, ES) 25 parts by weight of a compound I according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The composition has an active substance content of 25% by weight. v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of a compound I according to the inven- tion are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. The active substance content in the composition is 20% by weight. vi)Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of a compound I according to the invention are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as wa- ter-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solu- tion of the active substance. The composition has an active substance content of 50% by weight. vii) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
75 parts by weight of a compound I according to the invention are ground in a rotor- stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dispersion or solution of the active substance. The active substance content of the composition is 75% by weight. viii) Gel (GF)
In an agitated ball mill, 20 parts by weight of a compound I according to the invention are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained.
2. Composition types to be applied undiluted ix)Dustable powders (DP, DS)
5 parts by weight of a compound I according to the invention are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight. x) Granules (GR, FG, GG, MG) 0.5 parts by weight of a compound I according to the invention is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray- drying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5% by weight.
Xi)ULV solutions (UL) 10 parts by weight of a compound I according to the invention are dissolved in 90 parts by weight of an organic solvent, e. g. xylene. This gives a composition to be applied undiluted having an active substance content of 10% by weight.
The agrochemical compositions generally comprise between 0.01 and 95%, pref- erably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substances. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). Water-soluble concentrates (LS), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES) emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. In a preferred embodiment, the compounds or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
In a preferred embodiment, a suspension-type (FS) composition is used for seed treatment. Typcially, a FS composition may comprise 1-800 g/l of active substances, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water. The mixtures according to the invention can be used as such or in the form of their compositions, e. g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring. The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active substances according to the invention.
Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1 % by weight of active substance.
The active substances may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives. When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required. Thus, the invention also relates to plant propagation materials, preferably seeds, comprising the mixture according to the invention or a composition thereof in an amout as used for treatment thereof.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are, e. g., 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substances or the compositions com- prising them, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240®; alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®; EO/PO block polymers, e. g. Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates such as Lutensol XP 80®; and dioctyl sul- fosuccinate sodium such as Leophen RA®.
According to this invention, applying compound I together with at least one compound Il together is to be understood to denote, that compound I and at least one com- pound Il occur simultaneously at the site of action (i.e. the harmful fungi to be controlled or their habitats such as infected plants, plant propagation materials, particularly seeds, surfaces, materials or the soil as well as plants, plant propagation materials, particularly seeds, soil, surfaces, materials or rooms to be protected from fungal attack) in a fungicidally effective amount. This can be obtained by applying the compound I and at least one compound Il simultaneously, that is jointly (e. g. as tank-mix) or sper- ately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention. In such called binary mixtures according to the invention and compositions thereof comprising compound I (component 1 ) and one compound Il (component 2), the weight ratio of component 1 and component 2 generally depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :3 to 3:1.
In such called binary mixtures according to the invention and compositions thereof comprising compound I (component 1 ) and one compound Il (component 2), the weight ratio of component 1 and component 2 may also be in the range of from 1000:1 to 1 :10, preferably in the range of from 1000:1 to 1 :1 , more preferably in the range of from 1000:1 to 20:1 in particular in the range of from 1000:1 to 100:1.
The components of the compositions according to the invention can be used indi- vidually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts.
In one embodiment of the invention, the kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition. E. g., kits may include one or more fungicide component(s) and/or an adjuvant component and/or a insecticide component and/or a growth regulator component and/or a her- bicde. One or more of the components may already be combined together or pre- formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister. In other embodiments, two or more components of a kit may be packaged separately, i. e., not pre- formulated. As such, kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition. In both forms, a component of the kit may be applied separately from or together with the further components or as a component of a combination composition according to the invention for preparing the composition according to the invention.
The user applies the composition according to the invention usually from a predos- age device, a knapsack sprayer, a spray tank or a spray plane. Here, the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 50 to 500 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area, preferably 100 to 400 liters. According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising a mixture according to the invention and/or active substances from the groups A) to I), may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate (tank mix).
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising a mixture according to the invention and/or active substances from the groups A) to I), can be applied jointly (e. .g. after tankmix) or consecutively. The compositions according to the invention can, in the use form as fungicides, also be present together with other active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix). Mixing the mixtures according to the invention or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained. When preparing the mixtures and compositions thereof, it is preferred to employ the commercially available compositions of components 1 ) and 2), to which further compounds active against harmful fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active compounds or fertilizers may be added.
Usually, compositions comprising component 1 ) and 2), wherein component 2) consists of only one compound II, are employed. However, in certain cases compositions wherein component 2) consists of two or, if appropriate, more compounds Il may be advantageous.
Suitable further active components in the above sense are in particular the active compounds Il mentioned at the outset, and in particular the preferred compounds Il mentioned above.
Preference is also given to so called ternary mixtures comprising, in addition to component 1) and component 2) consisting of one active compound Il mentioned above, a further active compound V selected from active compound groups G) to P): The following list of active substances, in conjunction with which the compounds according to the invention can be used, is intended to illustrate the possible combinations but does not limit them: G) strobilurins azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, meto- minostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin, 2-(2-(6-(3-chloro-2-methyl-phenoxy)-5-fluoro-pyrimidin-4-yloxy)-phenyl)-2-methoxy- imino-N-methyl-acetamide, 3-methoxy-2-(2-(N-(4-methoxy-phenyl)-cyclopropane- carboximidoylsulfanylmethyl)-phenyl)-acrylic acid methyl ester, methyl (2-chloro- 5-[1 -(3-methylbenzyloxyimino)ethyl]benzyl)carbamate and 2-(2-(3-(2,6-di- chlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino- N-methyl-acetamide;
H) carboxamides
- carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fen- furam, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penthiopyrad, tecloftalam, thifluzamide, tiadinil, 2-amino-4-methyl-thiazole-5-carboxanilide,
2-chloro-N-(1 ,1 ,3-trimethyl-indan-4-yl)-nicotinamide, N-(2',4'-difluorobiphenyl-2-yl)- 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2',4'-dichlorobiphenyl- 2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2',5'-difluorobiphen- yl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2',5'-dichloro- biphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(3',5'-di- fluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(3'-fluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide,
N-(3'-chlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2'-fluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2'-chlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(3',5'-dichlorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-ca rbox- amide, N-(3',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-
4-carboxamide, N-(2',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyr- azole-4-carboxamide, N-[2-(1 ,1 , 2,3,3, 3-hexafluoropropoxy)-phenyl]-3-difluoro- methyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-[2-(1 ,1 ,2,2-tetrafluoroethoxy)- phenyl]-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(4'-trifluoromethyl- thiobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide,
N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carbox- amide, N-(4'-chloro-3',5'-difluoro-biphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyr- azole-4-carboxamide, N-(4'-chloro-3',5'-difluoro-biphenyl-2-yl)-3-trifluoromethyl- 1 -methyl-1 H-pyrazole-4-carboxamide, N-(3',4'-dichloro-5'-fluoro-biphenyl-2-yl)-
3-trifluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(3',5'-difluoro-4'-methyl- biphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(3',5'-difluo- ro-4'-methyl-biphenyl-2-yl)-3-trifluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-ca rbox- amide, N-(cis-2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-
4-carboxamide, N-^rans^-bicyclopropyl^-yl-pheny^-S-difluoromethyl-i-methyl- 1 H-pyrazole-4-carboxamide, N-[1 ,2,3,4-tetrahydro-9-(1 -methylethyl)-1 ,4-methano- naphthalen-5-yl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide;
- carboxylic morpholides: dimethomorph, flumorph; - benzoic acid amides: flumetover, fluopicolde, fluopyram, zoxamide, N-(3-Ethyl- 3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide;
- other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthio- farm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide;
J) azoles - triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusi- lazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobu- tanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1 ,2,4]triazol-1-yl)-cycloheptanol; imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizol; benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole; - others: ethaboxam, etridiazole, hymexazole and 2-(4-chloro-phenyl)-N-[4-(3,4-di- methoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
K) heterocyclic compounds
- pyridines: fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine,
2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyridine-2,6-di-carbo- nitrile, N-(1-(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4-dichloronicotinamide,
N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloro-nicotinamide; pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepani- pyrim, nitrapyrin, nuarimol, pyrimethanil; piperazines: triforine; pyrroles: fenpiclonil, fludioxonil; morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tride- morph; - piperidines: fenpropidin;
- dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin;
- non-aromatic 5-membered heterocycles: famoxadone, fenamidone, flutianil, octhili- none, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro-pyrazole- 1-carbothioic acid S-allyl ester; - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methyl- sulfate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quin- oxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propylchromen-4-one, 5-chloro- 1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 5-chloro-7-(4-methyl- piperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine, 6-(3,4-di- chloro-phenyl)-5-methyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-(4-tert-butyl- phenyl)-5-methyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 5-methyl-6-(3,5,5-tri- methyl-hexyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 5-methyl-6-octyl-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine-7-ylamine, 6-methyl-5-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine- 7-ylamine, 6-ethyl-5-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 5-ethyl-6-octyl-
[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 5-ethyl-6-(3,5,5-trimethyl-hexyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-propyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine- 7-ylamine, 5-methoxymethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-trifluoromethyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine and 5-trifluoro- methyl-6-(3,5,5-trimethyl-hexyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine;
L) carbamates
- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram;
- carbamates: benthiavalicarb, diethofencarb, flubenthiavalicarb, iprovalicarb, propa- mocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester; M) other fungicidally active substances - guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
- antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, poly- oxine, validamycin A; - nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fen- tin hydroxide;
- sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane;
- organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;
- organochlorine compounds: chlorothalonil, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quinto- zene, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide; - inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamin, metrafenone, mildiomycin, oxin-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N-(cyclo- propylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-
N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl- phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethyl- silanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl- 2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, 2-{1 -[2-(5-methyl-3-trifluoromethyl-pyrazole-1 -yl)-acetyl]-piperidin-4-yl}-thiazole-4- carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1-yl)-amide, 2-{1-[2-(5-meth- yl-S-trifluoromethyl-pyrazole-i-yO-acety^-piperidin^-ylJ-thiazole^-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide, acetic acid 6-tert.-butyl-8- fluoro-2,3-dimethyl-quinolin-4-yl ester and methoxy-acetic acid 6-tert-butyl-8-fluoro- 2,3-dimethyl-quinolin-4-yl ester.
N) growth regulators abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dike- gulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole; O) herbicides
- acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufena- cet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
- amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
- aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, ha- loxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl; - Bipyridyls: diquat, paraquat;
- (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, ep- tam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyribu- ticarb, thiobencarb, triallate;
- cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim;
- dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, triflura- lin;
- diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lac- tofen, oxyfluorfen; - hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil; imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, ima- zethapyr;
- phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop; - pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
- pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, pi- cloram, picolinafen, thiazopyr;
- sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlor- sulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfu- ron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, meso- sulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chloro-6-propyl- imidazo[1 ,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea; - triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, me- tamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
- ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, di- closulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, pe- noxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyrimi- nobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarba- zone,benfluresate, benzofenap, bentazone, benzobicyclon, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethlyl, chlorthal, cinme- thylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fentrazamide, flumi- clorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxa- ben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazo- ne, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembo- trione, thiencarbazone, topramezone, 4-hydroxy-3-[2-(2-methoxy-ethoxymethyl)-6- trifluoromethyl-pyridine-3-carbonyl]-bicyclo[3.2.1]oct-3-en-2-one, (3-[2-chloro-4- fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyπmidin-1-yl)- phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, θ-amino-δ-chloro^-cyclopropyl- pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl- phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2- carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine- 2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino- 2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester. P) insecticides
- organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, me- thidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, pa- raoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, pho- xim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbu- fos, triazophos, trichlorfon;
- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfen- valerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, te- fluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin; insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, no- valuron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozi- de, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
- nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, imida- cloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chloro-thiazol-5- ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane; - GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyraflupro- Ie, pyriprole, 5-amino-1-(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1 H-pyrazole-3- carbothioic acid amide; - macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram;
- mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim; - METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;
- Uncouplers: chlorfenapyr;
- oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; moulting disruptor compounds: cryomazine; - mixed function oxidase inhibitors: piperonyl butoxide;
- sodium channel blockers: indoxacarb, metaflumizone;
- others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, and pyrifluquinazon.
The present invention furthermore relates to agrochemical compositions comprising a mixture of compound I (component 1 ) and at least one compound Il (component 2) and at least one further active substance V useful for plant protection, e. g. selected from the groups G) to P) (component 3), in particular one further fungicide, e. g. one or more fungicide from the groups G) to M), as described above, and if desired one suitable solvent or solid carrier. Those mixtures are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi. Furthermore, combating harmful fungi with a mixture of compound I and at least one compound Il and at least one fungicide from groups G) to M), as described above, is more efficient than combating those fungi with a mixture of compound I and at least one compound Il or individual fungicides from groups G) to M) (synergistic mixtures).
In ternary mixtures, i.e. compositions according to the invention comprising compound I (component 1 ) and a compound Il (component 2) and a further active substance, (component 3), e. g. an active substance from groups G) to P), the weight ratio of component 1 and component 2 depends from the properties of the active substances used, preferably it is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1 , and the weight ratio of component 1 and component s preferably is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1. The active compounds V mentioned above, their preparation and their action against harmful fungi, insects or weeds are generally known (cf., for example, http://www.hclrss.demon.co.uk/index.html); they are commercially available. The compounds described by IUPAC nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031 ; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ;
EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624).
Preference is given to ternary mixtures of components 1 ) and 2) with an active compound V selected from the group of the azoles G). Preference is also given to ternary mixtures of components 1) and 2) with an active compound V selected from the group of the strobilurins H).
Preference is given to ternary mixtures of components 1 ) and 2) with an active compound V selected from the group of the carboxamides J).
Preference is furthermore also given to ternary mixtures of components 1) and 2) with an active compound V selected from the group of the heterocyclic compounds K).
Preference is furthermore also given to ternary mixtures of components 1) and 2) with an active compound V selected from the group of the carbamates L).
Preference is furthermore also given to ternary mixtures of components 1) and 2) with an active compound selected from the group of the other fungicides M). Preference is furthermore also given to ternary mixtures compositions of components 1 ) and 2) with an active compound selected from the group of the azoles G) selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl, carbendazim and ethaboxam, more preferably selected from the group consisting of epoxiconazole, fluquinconazole, flutriafol, metconazole, tebuconazole, triticonazole, prochloraz and carbendazim.
Preference is also given to ternary mixtures of components 1) and 2) with at least one active compound selected from the group of the strobilurins H) selected from the group consisting of azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin, more preferably selected from kresoxim-methyl, orysastrobin and pyraclostrobin, in particular pyraclostrobin.
Preference is also given to ternary mixtures of components 1) and 2) with an active compound selected from the group of the carboxamides J) selected from the group consisting of fenhexamid, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolide (picobenzamid), zoxamide, carpropamid and mandipropamid, more preferably selected from fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, zoxamide and carpropamid.
Preference is also given to ternary mixtures of components 1) and 2) with an active compound selected from the group of the heterocyclic compounds J) selected from the group consisting of fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquinazid, acibenzolar-S-methyl, captafol, folpet, fenoxanil and quinoxyfen, in particular fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fenpropimorph, tride- morph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquinazid, acibenzolar-S-methyl, captafol, folpet, fenoxanil and quinoxyfen.
Preference is also given to ternary mixtures of components 1) and 2) with an active compound selected from the group of the heterocyclic compounds K) selected from the group consisting of pyrimethanil, dodemorph, fenpropimorph, tridemorph, iprodione, vinclozolin and quinoxyfen, in particular pyrimethanil, dodemorph, fenpropimorph, tridemorph, iprodione, vinclozolin and quinoxyfen.
Preference is also given to ternary mixtures of components 1) and 2) with at least one active compound selected from the group of the carbamates L) selected from the group consisting of mancozeb, metiram, propineb, thiram, iprovalicarb, flubenthiavali- carb and propamocarb preferably selected from mancozeb and metiram. Preference is also given to ternary mixtures of components 1) and 2) with an active compound selected from the group of the other fungicides M) selected from the group consisting of dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, chlorothalonil, dichlofluanid, thiophanate-methyl, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur, cymoxanil and spiroxamine, preferably selected from dithianon, phosphorous acid and its salts and chlorothalonil.
Use examples
The fungicidal action of components 1 ) and 2) and of the mixtures according to the invention was demonstrated by the tests below.
The active compounds were formulated separately as a stock solution of a concentration of 10 000 ppm in DMSO.
Use example 1 - Activity against the late blight pathogen Phytophthora infestans in the microtiter test
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Phytophtora infestans containing a pea juice-based aqueous nutrient medium was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
The measured parameters were compared to the growth of the active compound- free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies. An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing.
The expected efficacies of active compound mixtures were determined using Colby's formula [R. S. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacies.
Figure imgf000035_0001
The test results show that, by virtue of the synergism, the mixtures according to the invention are considerabley more effective than had been predicted using Colby's for- mula, different from mixtures known in the art used in the comparative trial.

Claims

34Claims
1. A fungicidal mixture, comprising
1 ) 2-[(2-fluoro-5-trifluoromethyl)phenylthio]-2-[3-(2-methoxyphenyl)- I
Figure imgf000036_0001
and
2) at least one compound Il selected from groups A) to F):
A) strobilurins dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxy- strobin, pyraclostrobin, pyribencarb, trifloxystrobin;
B) carboxamides
- carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flutolanil, furametpyr, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penthiopyrad, teclof- talam, thifluzamide, tiadinil, 3-dfluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid-(3',4',5'-trifluorobiphenyl-2-yl)-amide, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3- dimethyl-5-fluoro-1 H-pyrazole-4-carboxylic acid amide
N-(2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide, N-(trans-2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1-methyl-1 H- pyrazole-4-carboxylic acid amide, N-(cis-2-bicyclopropyl-2-yl-phenyl)-3- difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide;
- carboxylic morpholides: dimethomorph, flumorph;
- benzoic acid amides: flumetover, fluopicolde, fluopyram, zoxamide;
- other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracyclin and silthiofarm;
C) azoles
- triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenocona- zole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, imibenconazole, ipconazole, metconazole, myclobutanil, oxpo- 35 conazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simecona- zole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, unicona- zole;
- imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizol; - benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;
- others: ethaboxam, etridiazole, hymexazole and 2-(4-chloro-phenyl)-N-[4-(3,4-di- methoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
D) heterocyclic compounds - pyridines: fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-
3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine;
- pyrimidines: bupirimate, diflumetorim, fenarimol, ferimzone, mepanipyrim, ni- trapyrin, nuarimol, pyrimethanil;
- piperazines: triforine; - pyrroles: fenpiclonil, fludioxonil;
- morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tride- morph;
- piperidines: fenpropidin, 2-{1-[2-(5-Methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]- piperidin-4-yl}-thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1- yl)-amide, 2-{1 -[2-(5-Methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}- thiazole-4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide;
- dicarboximides: fluoroimid, iprodione, proxymidone, vinclozolin;
- non-aromatic 5-membered heterocycles: famoxadone, fenamidone, octhilinone, probenazole; - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, cap- tan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat- methylsulfate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propylchromen-4-one, 5- ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, 6-octyl-5-propyl-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine-7-ylamine, and 6-octyl-5-trifluoromethyl-[1 ,2,4]triazolo[1 ,5- a]pyrimidine-7-ylamine;
E) carbamates
- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulpho- carb, metiram, propineb, thiram, zineb, ziram;
- carbamates: benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)- but-2-yl) carbamic acid-(4-fluorophenyl) ester;
F) other active substances
- guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, 36 iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
- antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, polyoxine, validamycin A;
- nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fen- tin hydroxide;
- sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane;
- organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iproben- fos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;
- organochlorine compounds: dichlofluanid, dichlorophen, flusulfamide, hexa- chlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quintozene, thiophanate-methyl, tolylfluanid;
- inorganic active substances: Bordeaux mixture, copper acetate, copper hydrox- ide, copper oxychloride, basic copper sulfate, sulfur;
- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamin, metrafenone, mildiomycin, oxin-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N'-(4-(4- chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl forma- midine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N- methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)- phenyl)-N-ethyl-N-methyl formamidine and N'-(5-difluoromethyl-2-methyl-4-(3-tri- methylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine; in a synergistically effective amount.
A mixture according to claim 1 , comprising as component 2) at least one compound Il selected from groups A) to F):
A) strobilurins dimoxystrobin, enestroburin, fluoxastrobin, orysastrobin, picoxystrobin, pyribencarb;
B) carboxamides
- carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, fenfuram, fenhexamid, isotianil, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxa- dixyl, oxycarboxin, penthiopyrad, tecloftalam, tiadinil, 3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxylic acid-(3',4',5'-trifluorobiphenyl-2-yl)-amide, N-(2-(1 ,3-di- methyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxylic acid amide, N-(2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide, N-(trans-2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1-methyl-1 H-py- razole-4-carboxylic acid amide, N-(cis-2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl- 1-methyl-1 H-pyrazole-4-carboxylic acid amide;
- carboxylic morpholides: flumorph; 37
- benzoic acid amides: flumetover, fluopicolde, fluopyram, zoxamide;
- other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracyclin and silthiofarm;
C) azoles
- triazoles: azaconazole, flusilazole, ipconazole, myclobutanil, oxpoconazole, pa- clobutrazole, penconazole, simeconazole, triticonazole, uniconazole;
- imidazoles: imazalil, pefurazoate, prochloraz, triflumizol;
- benzimidazoles: fuberidazole; - others: ethaboxam, etridiazole, hymexazole and 2-(4-chloro-phenyl)-N-[4-(3,4-di- methoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
D) heterocyclic compounds
- pyridines: pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine;
- pyrimidines: bupirimate, diflumetorim, fenarimol, ferimzone, nitrapyrin, nuarimol;
- piperazines: triforine;
- morpholines: aldimorph, dodemorph, dodemorph-acetate;
- piperidines: 2-{1 -[2-(5-Methyl-3-trifluoromethyl-pyrazol-1 -yl)-acetyl]-piperid in-4-yl}- thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1-yl)-amide, 2-{1-
[2-(5-Methyl-3-trifluoromethyl-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4- carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide;
- dicarboximides: vinclozolin;
- non-aromatic 5-membered heterocycles: octhilinone; - others: acibenzolar-S-methyl, amisulbrom, blasticidin-S, chinomethionat,, deba- carb, diclomezine, difenzoquat, difenzoquat-methylsulfate, fenoxanil, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6- iodo-3-propylchromen-4-one, 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine- 7-ylamine, 6-octyl-5-propyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, and 6-octyl-5- trifluoromethyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine;
E) carbamates
- thio- and dithiocarbamates: ferbam, metam, methasulphocarb, metiram, propineb, ziram; - carbamates: propamocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4- cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
F) other active substances
- guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate; - antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, polyoxine, validamycin A; 38
- nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fen- tin hydroxide; - sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane;
- organophosphorus compounds: edifenphos, iprobenfos, phosphorous acid and its salts;
- organochlorine compounds: dichlorophen, flusulfamide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, quintozene, tolylfluanid; - inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamin, metrafenone, mildiomycin, oxin-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N'-(4-(4- chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl forma- midine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N- methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)- phenyl)-N-ethyl-N-methyl formamidine and N'-(5-difluoromethyl-2-methyl-4-(3-tri- methylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine; in a synergistically effective amount.
3. A mixture according to claim 1 , comprising as component 2) at least one compound selected from dimoxystrobin, enestroburin, fluoxastrobin and orysastrobin.
4. A mixture according to claim 1 , comprising pyraclostrobin as component 2).
5. A mixture according to claim 1 , comprising as component 2) at least one compound Il selected from benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, car- propamid, dicyclomet, fenfuram, fenhexamid, flumorph, flumetover, fluopicolde, fluopyram, isotianil, kiralaxyl, mandiproamid, metalaxyl, metalaxyl-M (mefenox- am), ofurace, oxadixyl, oxycarboxin, oxytetracyclin, penthiopyrad, silthiofarm, te- cloftalam, tiadinil, zoxamide, 3-dfluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid-(3',4',5'-trifluorobiphenyl-2-yl)-amide, N-(2-(1 ,3-dimethyl-butyl)-phenyl)- 1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxylic acid amide, N-(2-bicyclopropyl- 2-yl-phenyl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide, N-(trans-2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-
4-carboxylic acid amide, and N-(cis-2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl- 1 -methyl-1 H-pyrazole-4-carboxylic acid amide.
6. A mixture according to claim 1 , comprising as component 2) at least one com- pound Il selected from bixafen, boscalid, penthiopyrad, 3-difluoromethyl-
1 -methyl-1 H-pyrazole-4-carboxylic acid-(3',4',5'-trifluorobiphenyl-2-yl)-amide, 39
N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxylic acid amide, N-(2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1-methyl-1 H-pyra- zole-4-carboxylic acid amide, N-(trans-2-bicyclopropyl-2-yl-phenyl)-3-difluoro- methyl-1-methyl-1 H-pyrazole-4-carboxylic acid amide and N-(cis-2-bicyclopropyl- 2-yl-phenyl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid amide.
7. A mixture according to claim 6, comprising 3-difluoromethyl-1 -methyl-1 H-pyra- zole-4-carboxylic acid-(3',4',5'-trifluorobiphenyl-2-yl)-amide as component 2).
8. A mixture according to claim 1 , comprising dimethomorph as component 2).
9. A mixture according to claim 1 , comprising as component 2) at least one compound Il selected from azaconazole, benomyl, carbendazim, cyazofamid, eth- aboxam, etridiazole, fuberidazole, hymexazole, imazalil, ipconazole, myclobu- tanil, oxpoconazole, paclobutrazole, penconazole, pefurazoate, prochloraz, pro- thioconazole, simeconazole, thiabendazole, triflumizol, triticonazole, uniconazole and 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyl- oxy-acetamide.
10. A mixture according to claim 1 , comprising as component 2) at least one compound Il selected from acibenzolar-S-methyl, amisulbrom, aldimorph, blasticidin- S, bupirimate, chinomethionat, debacarb, diclomezine, difenzoquat, difenzoquat- methylsulfate, diflumetorim, dodemorph, dodemorph-acetate, fenarimol, fenox- anil, ferimzone, nitrapyrin, nuarimol, octhilinone, oxolinic acid, piperalin, proquin- azid, proxymidone, pyrifenox, triforine, pyroquilon, quinoxyfen, triazoxide, tricy- clazole, vinclozolin, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 2-{1-[2-(5-methyl- S-trifluoromethyl-pyrazol-i-yO-acety^-piperidin^-ylJ-thiazole^-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1 -yl)-amide, 2-{1 -[2-(5-methyl-3-trifluoro- methyl-pyrazol-i-yO-acety^-piperidin^-ylJ-thiazole^-carboxylic acid methyl-
(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide and 2-butoxy-6-iodo-3-propyl- chromen-4-one.
1 1. A mixture according to claim 1 , comprising as component 2) 5-ethyl-6-octyl- [1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine.
12. A mixture according to claim 1 , comprising as component 2) at least one active compound Il selected from metrafenone and prohexadione-calcium.
13. A mixture according to claim 1 , comprising dithianon as component 2). 40
14. A mixture according to any of the claims 1 to 14, wherein the weight ratio of component 1 and component 2 is in the range of from 1000:1 to 1 :10.
15. A composition comprising at least one solvent or solid carrier and a mixture ac- cording to any of claims 1 to 14.
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