WO2008092818A2 - Pesticidal mixtures - Google Patents

Pesticidal mixtures Download PDF

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WO2008092818A2
WO2008092818A2 PCT/EP2008/050927 EP2008050927W WO2008092818A2 WO 2008092818 A2 WO2008092818 A2 WO 2008092818A2 EP 2008050927 W EP2008050927 W EP 2008050927W WO 2008092818 A2 WO2008092818 A2 WO 2008092818A2
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compounds
alkyl
methyl
cio
halogen
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PCT/EP2008/050927
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French (fr)
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WO2008092818A3 (en
Inventor
Markus Bold
Clark Dennis Klein, Jr.
Hassan Oloumi-Sadeghi
David G. Kuhn
Reinhard Stierl
Jürgen LANGEWALD
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Basf Se
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Publication of WO2008092818A3 publication Critical patent/WO2008092818A3/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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • Pesticidal mixtures Description The present invention relates to pesticidal mixtures comprising, as active components, 1 ) an amidrazone of the formula I
  • R is hydrogen, d-C ⁇ -alkyl, d-C ⁇ -alkoxycarbonyl, d-C ⁇ -alkylaminocarbonyl, or di(Ci-C6-alkyl)-aminocarbonyl,
  • alkyl group is unsubstituted or substituted with 1 to 3 substituents independently selected from halogen, cyano, nitro, d-C ⁇ -alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-C ⁇ -haloalkoxy, d-C ⁇ -alkylthio, d-Ce-haloalkylthio, d-Ce-alkylsulfonyl, Ci-C 6 -alkylsulfinyl, and di(Ci-C6alkyl)-amino;
  • R 1 and R 2 are each independently hydrogen, Ci-Cio-alkyl, C3-Cio-alkenyl,
  • C3-Cio-alkynyl C3-Ci2-cycloalkyl, Ci-C ⁇ -alkylamino, di(d-Ce-alkyl)- amino, Ci-C ⁇ -alkylcarbonylamino, Ci-C ⁇ -alkylsulfonyl, or
  • alkyl, alkenyl, alkynyl or cycloalkyl groups are unsubstituted or substituted with 1 to 3 substituents independently selected from halogen, nitro, cyano, d-C ⁇ -alkoxy, C-i-C ⁇ -haloalkoxy, C-i-C ⁇ -alkylthio, d-Ce-haloalkylthio, d-Ce-alkylsulfonyl, d-Ce-alkylsulfinyl, Ci-C ⁇ -haloalkylsulfonyl, Ci-C6-haloalkylsulfinyl, C3-C6-cycloalkyl, phenyl, and pyridyl;
  • R 3 is d-do-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, C3-Ci2-cycloalkyl, wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups are unsubstituted or partially or fully halogenated and/or substituted with
  • substituents independently selected from cyano, nitro, hydroxy, mercapto, amino, Ci-C ⁇ -alkyl, Cs-C ⁇ -cycloalkyl, d-C ⁇ -alkoxy, Ci-C ⁇ -alkylamino, di(Ci-C6-alkyl)-amino, C-i-C ⁇ -alkylthio, Ci-C ⁇ -alkylsulfonyl, and Ci-C ⁇ -alkylsulfinyl, or
  • a 3- to 6-membered saturated or partially unsaturated ring which may contain 1 to 3 heteroatoms selected from oxygen, sulfur and nitrogen, and which is unsubstituted or substituted with 1 to 5 substituents independently selected from halogen, Ci-C ⁇ -alkyl, C-i-C ⁇ -alkylthio, Ci-C ⁇ -alkylsulfonyl, Ci-C ⁇ -alkylsulfinyl, Ci-C ⁇ -alkoxy, C-i-C ⁇ -haloalkoxy, nitro and cyano, wherein in each of the above radicals the alkyl group is unsubstituted or substituted with 1 to 3 halogen atoms;
  • A is C-R 4 or N
  • R 4 , R 5 , R 6 are each independently hydrogen, halogen, nitro, cyano, amino, mercapto, hydroxy, Ci-Cio-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl,
  • Ci-C ⁇ -alkoxy Ci-C ⁇ -alkylamino, di(Ci-C6-alkyl)- amino, C-i-C ⁇ -alkylthio, Ci-C ⁇ -alkylsulfonyl, Ci-C ⁇ -alkylsulfinyl, or a 5- to 6-membered aromatic ring which may contain 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen;
  • Y is hydrogen, halogen, cyano, nitro, amino, hydroxy, mercapto, Ci-C ⁇ -alkyl,
  • n O, 1 , or 2;
  • fungicidal compound Il selected from the following groups: A) azoles, in particular: bitertanol, bromuconazole, cyproconazole, difeno- conazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fen- buconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipcona- zole, metconazole, myclobutanil, penconazole, propiconazole, prothiocona- zole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole; prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid; benomyl, carbendazim, thiabendazole,
  • B) strobilurins in particular: azoxystrobin, dimoxystrobin, enestroburin, fluoxa- strobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, or methyl (2-chloro-5-[1-(3-methylbenzyloxy- imino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1 -(6-methylpyridin-2-yl- methoxyimino)ethyl]benzyl)carbamate, methyl 2-(ortho-((2,5-dimethylphe- nyloxymethylene)phenyl)-3-methoxyacrylate;
  • carboxamides in particular: carboxin, benalaxyl, boscalid, fenhexamid, flu- tolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, N-(4'-bromobiphenyl-2-yl)-
  • heterocylic compounds in particular: fluazinam, pyrifenox; bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil; triforine; fenpiclonil, fludioxonil; aldimorph, dodemorph, fenpropimorph, tridemorph; fenpropidin, iprodione, procymidone, vinclozolin; famoxadone, fenamidone, octhilinone, probenazole; amisulbrom, anilazine, diclomezine, pyroquilon, proquinazid, tricyclazole; 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine,
  • E) carbamates in particular: mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram; benthiavalicarb, diethofencarb, iprovalicarb, flubenthiavalicarb, propamocarb; methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methyl- butyrylamino)propanoate; and F) other active compounds, selected from guanidines: dodine, iminoctadine, guazatine; antibiotics: kasugamycin, streptomycin, polyoxine, validamycin A; nitrophenyl derivates: binapacryl, dinocap, dinobuton; sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane; organometal compounds: fentin salts, such as fentin-acetate; organophosphorus compounds:
  • the invention relates to a method for controlling pests, using mixtures of a compound I with active compounds Il and to the use of the compounds I with the active compounds Il for preparing such mixtures, and also to compositions comprising such mixtures.
  • the term "pest” is considered to include any harmful organisms including insects, acarids, nematodes, and phytopathogenic fungi.
  • the invention relates to a method for controlling phytopathogenic harmful fungi using mixtures of a compound I with active compounds Il and to the use of a compound I with active compounds Il for preparing such mixtures, and also to compositions com- prising these mixtures.
  • the present invention provides methods for the control of insects, acarids or nematodes comprising contacting the insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with a pesticidally effective amount of mixtures of a compound I with one or more compounds II.
  • the present invention also relates to a method of protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or the soil or water in which the plant is growing, with a pesticidally effec- tive amount of a mixture of a compound I with one or more compounds 11.
  • This invention also provides a method for treating, controlling, preventing or protecting a warm-blooded animal or fish against infestation or infection by insects, acarids or nematodes which comprises orally, topically or parenterally administering or applying to the animal or fish a pesticidally effective amount of a mixture of a compound I with one or more compounds II.
  • the invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting a warm-blooded animal or a fish against infestation or infection by insects, acarids or nematodes which comprises a pesticidally effective amount of a mixture of a compound I with one or more compounds II.
  • amidrazones of formula I referred to above as component 1 , their preparation and their action against insect and acarid pests are known (cf. for example, EP-A 604 798, J. A. Furch et al., "Amidrazones: A New Class of Coleopteran Insecticides", ACS Symposium Series 686, Am. Chem. Soc, 1998, Chapter 18, pp. 178; and D. G. Kuhn et al., "Cycloalkyl-substituted Amidrazones: A Novel Class of Insect Control Agents", ACS Symposium Series 686, Am. Chem. Soc, 1998, Chapter 19, pp. 185).
  • the amidrazones of formula I can be obtained by the preparation methods as described or refer- enced in EP-A 604 798.
  • an alternative route for their preparation is disclosed in co-pending European patent application No. 06118365.3 filed on August 3, 2006.
  • WO 2006/128863 A1 discloses mixtures of the amidrazones of formula I with certain insecticides. In general, mixtures of the amidrazones I with a fungicide, and their favourable synergistic effect are not known from the prior art.
  • the active compounds Il mentioned above as component 2 their preparation and their action against harmful fungi are generally known (cf.: http://www.hclrss.demon.co.uk/index.html); they are commercially available. Paticu- larly, they are known from: bitertanol, ⁇ -([1 ,1 '-biphenyl]-4-yloxy)- ⁇ -(1 ,1-dimethylethyl)- 1 H-1 ,2,4-triazole-1-ethanol (DE 23 24 020), bromuconazole, 1-[[4-bromo-2-(2,4-di- chlorophenyl)tetrahydro-2-furanyl]methyl]-1 H-1 ,2,4-triazole (Proc.
  • epoxiconazole (2RS,3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophe- nyl)propyl]-1 H-1 ,2,4-triazole (EP-A 196 038); fluquinconazole, 3-(2,4-dichlorophenyl)-6- fluoro-2-[1 ,2,4]-triazol-1-yl-3H-quinazolin-4-one (Proc. Br. Crop Prot.
  • aldimorph 4-alkyl-2,5(or 2,6)-dimethylmorpholine, comprising 65-75% of 2,6-di- methylmorpholine and 25-35% of 2,5-dimethylmorpholine, comprising more than 85% of 4-dodecyl-2,5(or 2,6)-dimethylmorpholine, where "alkyl” may also include octyl, de- cyl, tetradecyl or hexadecyl and where the cis/trans ratio is 1 :1 ; dodemorph, 4-cyclo- dodecyl-2,6-dimethylmorpholine (DE 1 198125); fenpropimorph, (RS)-cis-4-[3-(4-tert- butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine (DE 27 52 096); tridemorph, 2,6- dimethyl-4-tridecylmorpholine (DE 1 1 64 152);
  • Pesticide Inf. No. 2, S. 1 1 (1970)); fo- setyl, fosetyl-aluminum, (aluminum) ethylphosphonate (FR 22 54 276); pyrazophos, ethyl 2-diethoxyphosphinothioyloxy-5-methylpyrazolo[1 ,5-a]pyrimidine-6-carboxylate (DE 15 45 790); tolclofos-methyl, 0-2,6-dichloro-p-tolyl 0,0-dimethyl phosphorothioate (GB 14 67 561); chlorothalonil, 2,4,5,6-tetrachloroisophthalonitrile (US 3 290 353); di- chlofluanid, N-dichlorofluoromethylthio-N,N-dimethyl-N-phenylsulfamide (DE 1 1 93 498); flusulfamide, 2',4-dichloro- ⁇ , ⁇ , ⁇ -
  • One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control.
  • Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests.
  • the compounds I and Il can be applied simul- taneously, that is jointly (e.g. in the same formulation) or separately (e.g. in different formulations, such as in kit form), or in succession. If there is a sucessive application, it will also be appreciated that the subsequently applied compounds I and Il should be applied to a subject (e.g. the pest, plant or animal) within a time scale so as to achieve or optimize the above referred to advantageous synergistic effect.
  • a subject e.g. the pest, plant or animal
  • Halogen will be taken to mean fluorine, chlorine, bromine, and iodine.
  • halo refers to fluoro, chloro, bromo, and iodo.
  • alkyl refers to a branched or unbranched saturated hydro- carbon group having 1 to 10 carbon atoms, especially d-C ⁇ -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-di
  • haloalkyl refers to a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C2-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, tri- chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichloro- fluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-
  • alkoxy and “alkylthio” refer to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group. Examples include methoxy, ethoxy, pro- poxy, isopropoxy, methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.
  • alkylamino refers to a nitrogen atom which carries 1 or 2 straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above) which may be the same or different. Examples include methylamino, dimethylamino, ethylamino, di- ethylamino, methylethylamino, isopropylamino, or methylisopropylamino.
  • alkenyl intends a branched or unbranched unsaturated hydrocarbon group having 3 to 10 carbon atoms and a double bond in any position, such as C3-C6 alkenyl such as 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl; 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1- butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2- butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1-dimethyl-2-propenyl, 1
  • alkynyl refers to a branched or unbranched unsaturated hydrocarbon group containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl and the like.
  • Cycloalkyl refers to a monocyclic 3- to 8-, 10- or 12-membered saturated carbon atom rings, e.g. Cs-Cs-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • aryl refers to an aromatic carbocyclic group having at least one aromatic ring (e.g., phenyl or biphenyl) or multiple condensed rings in which at least one ring is aromatic (e.g., 1 ,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl), each of which may be substituted.
  • a 5- to 6-membered aromatic ring containing 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen intends e.g. 5-membered heteroaryl, containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom, e.g.
  • a 3- to 6-membered saturated or partially unsaturated ring which contains 1 to 3 het- eroatoms selected from oxygen, sulfur and nitrogen intends e.g. a saturated 3- to 6- membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, such as aziridine, pyrrolidine, tetrahydrofuran, tetrahydropyran, or piperidine.
  • A denotes C-R 4 .
  • B denotes C-R 5 .
  • W denotes C-R 6 .
  • A denotes C-R 4
  • B denotes C-R 5
  • W denotes C-R 6 .
  • R 4 is halogen or d-C ⁇ -haloalkyl, preferably halogen, especially chlorine or bromine, with chlorine being most preferred.
  • R 5 is hydrogen or halogen, especially hydrogen.
  • R 6 is halogen or C-i-C ⁇ -haloalkyl, preferably Ci-C ⁇ -haloalkyl, especially trifluoromethyl.
  • Y is halogen or C-i-C ⁇ -haloalkyl, in particular halogen or C-i-C ⁇ -haloalkyl which is disposed in the 6-position.
  • Y is halogen, especially chlorine.
  • Y is halogen, in particular chlorine, which is disposed in the 6-position.
  • n is 1.
  • R denotes hydrogen or d-C ⁇ -alkyl, in particular hydrogen.
  • R 1 and R 2 are each independently hydro- gen, Ci-Cio-alkyl which is unsubstituted or substituted by Ci-C4-alkoxy, or
  • R 1 and R 2 are each independently hydrogen, Ci-C4-alkyl, or Cs-C ⁇ -cycloalkyl.
  • R 1 is hydrogen and R 2 is Ci-Cio-alkyl which is unsubstituted or substituted by Ci-C4-alkoxy, or C3-Cio-cycloalkyl which is unsubstituted or substituted with from 1 to 3 halogen.
  • R 1 is hydrogen and R 2 is Ci-C4-alkyl or C3-C6-cycloalkyl.
  • R 1 is hydrogen and R 2 is Ci-C4-alkyl, in particular ethyl.
  • R 3 is unsubstituted Ci-Cio-alkyl or C3-Cio-cycloalkyl, which is unsubstituted or substituted with 1 to 5 halogen atoms and/or 1 to 3 d-C ⁇ -alkyl groups.
  • R 3 is Ci-Cio-alkyl, in particular C-i-C ⁇ -alkyl, with tert-butyl being the most preferred.
  • R 3 is cyclopropyl which is unsubstituted or substituted with d-C ⁇ -alkyl or halogen.
  • R 3 is C3-Cio-cycloalkyl which is unsubstituted or substituted with 1 to 5 halogen atoms and/or 1 to 3 d-C ⁇ -alkyl groups and/or 1 to 3 Ci-C ⁇ -haloalkyl groups.
  • R 3 is cyclopropyl which is unsubstituted or substituted with 1 to 3 halogen atoms and/or 1 to 3 d-C ⁇ -alkyl groups and/or 1 to 3 Ci-C ⁇ -haloalkyl groups.
  • R 3 is cyclopropyl which is substituted with 2 halogen atoms and/or 1 d-C ⁇ -alkyl group, in particular cyclopropyl which is substituted with 2 chlorine atoms and/or 1 methyl group.
  • R 3 is a cyclopropyl group of formula III
  • R 7 is hydrogen, Ci-C 6 -alkyl or Ci-C 6 -haloalkyl
  • R 8 , R 9 , R 10 and R 11 are each independently selected from hydrogen, halogen, d-C ⁇ -alkyl and d-C ⁇ -haloalkyl.
  • R 3 is a cyclopropyl group of formula III wherein R 7 is hydrogen, d-C ⁇ -alkyl or C-i-C ⁇ -haloalkyl, R 8 and R 9 are both halogen, and R 10 and R 11 are both hydrogen.
  • R 3 is a cyclopropyl group of formula III wherein R 7 is d-C ⁇ -alkyl, R 8 and R 9 are both halogen, and R 10 and R 11 are both hydro- gen.
  • R 3 is a cyclopropyl group of formula III wherein R 7 is hydrogen, methyl or trifluoromethyl, R 8 and R 9 are independently selected from fluoro, chloro and bromo, and R 10 and R 11 are both hydrogen.
  • R 3 is a cyclopropyl group of formula III wherein R 7 is hydrogen or methyl, R 8 and R 9 are chloro or bromo, and R 10 and R 11 are both hydrogen.
  • R 3 is a cyclopropyl group of formula III wherein R 7 is methyl, R 8 and R 9 are chloro or bromo, and R 10 and R 11 are both hydrogen, in particular a cyclopropyl group of formula III wherein R 7 is methyl, R 8 and R 9 are both chloro, and R 10 and R 11 are both hydrogen, i.e. 1-(2,2-dichloro-1- methylcyclopropyl).
  • R 5 , R 6 and Y n corresponds in each case to a row of Table A.
  • R 4 , R 5 , R 6 and Y n corresponds in each case to a row of Table A.
  • R 6 is chlorine or trifluoromethyl
  • R 4 and Y are each independently chlorine or bromine
  • R 2 is C-i-Ce-alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, or
  • R 3 is Ci-C ⁇ -alkyl or a cyclopropyl group of formula III as defined herein wherein R 7 is hydrogen, d-Ce-alkyl or Ci-C 6 -haloalkyl, and R 8 , R 9 , R 10 and R 11 are each independently selected from hydrogen, halogen, Ci-C ⁇ -alkyl and C-i-C ⁇ -haloalkyl.
  • R 6 is trifluoromethyl.
  • Y and R 4 are both chlorine.
  • R 2 is Ci-C ⁇ -alkyl, especially ethyl.
  • R 3 is Ci-C ⁇ -alkyl, in particular tert-butyl.
  • R 3 is cyclopropyl which is unsubstituted or substituted by 1 to 3 halogen atoms. In a further embodiment of the compounds I-B, R 3 is cyclopropyl which is substituted by 2 halogen atoms, especially chlorine and bromine, and 1 d-C ⁇ -alkyl group, especially methyl.
  • R 3 is a cyclopropyl group of formula III wherein R 7 is hydrogen, d-C ⁇ -alkyl or d-C ⁇ -haloalkyl, R 8 and R 9 are both halogen, and R 10 and R 11 are both hydrogen.
  • R 3 is a cyclopropyl group of formula III wherein R 7 is d-C ⁇ -alkyl, R 8 and R 9 are both halogen, and R 10 and R 11 are both hydrogen.
  • R 3 is a cyclopropyl group of formula III wherein R 7 is hydrogen, methyl or trifluoromethyl, R 8 and R 9 are independently selected from fluoro, chloro and bromo, and R 10 and R 11 are both hydrogen.
  • R 3 is a cyclopropyl group of formula III wherein R 7 is hydrogen or methyl, R 8 and R 9 are chloro or bromo, and R 10 and R 11 are both hydrogen.
  • R 3 is a cyclopropyl group of formula III wherein R 7 is methyl, R 8 and R 9 are chloro or bromo, and R 10 and R 11 are both hydrogen.
  • R 3 is a cyclopropyl group of formula III wherein R 7 is methyl, R 8 and R 9 are both chloro, and R 10 and R 11 are both hydrogen, i.e. 1 -(2,2-dichloro-1 -methylcyclopropyl).
  • R 6 is trifluoromethyl
  • Y and R 4 are each independently chlorine or bromine
  • R 2 is d-C ⁇ -alkyl
  • R 3 is d-C ⁇ -alkyl or Cs-C ⁇ -cycloalkyl which is substituted by 1 or 2 halogen atoms and 1 d-Ce-alkyl.
  • Agrochemically acceptable salts of the amidrazones of formula I can also be used in the present invention, such as, for example, conventional salts formed from suitable organic or inorganic acids.
  • agrochemically acceptable salts of the compounds of formula I include chlorides, bromides, fluorides, hydrogen sulfates, sulfates, dihydrogen phosphates, hydrogen phosphates, phosphates, nitrates, hydrogen carbonates, carbonates, hexafluorosilicates, hexafluorophosphates, benzoates, and the salts of Ci-C4-alkanoic acids, preferably formates, acetates, propionates and butyrates.
  • the scope of the present invention includes isomers of the amidrazones of formula I as defined herein.
  • the term "isomer” is used herein in its broadest sense to include structural isomers (such as, for example, positional isomers and tautomers) and stereoisomers (such as, for example, optical isomers, rotational isomers and E/Z isomers).
  • the amidrazones of formula I possess asymmetric carbon atoms
  • the ra- cemates and diastereomers as well as the individual enantiometric forms of the amidrazones I as described herein also form part of the scope of the present invention.
  • mixtures according to the invention relate to combinations of one of the compounds of Tables 1 to 14, in particular one of the pre- ferred compounds I hereinabove, and one of the following active compounds II:
  • A) azoles such as cyproconazole, difenoconazole, fluquinconazole, flusilazole, metconazole, propiconazole, prothioconazole, tebuconazole prochloraz, cyazofamid; carbendazim; ethaboxam;
  • B) strobilurins such as azoxystrobin, enestroburin, fluoxastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin or methyl (2-chloro-5-[1-(3- methylbenzyloxyimino)-ethyl]benzyl)carbamate, methyl (2-chloro-5-[1 -(6- methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate;
  • carboxamides such as benalaxyl, boscalid, fenhexamid, metalaxyl, ofurace, oxadixyl, dimethomorph; fluopicolide (picobenzamid), zoxamide; mandipropamid;
  • heterocylic compounds such as fluazinam; cyprodinil, pyrimethanil; dodemorph, iprodione, vinclozolin; famoxadone, fenamidone; amisulbrom;
  • carbamates such as mancozeb, maneb, metiram, propineb; benthiavalicarb, iprovalicarb, flubenthiavalicarb; methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methyl- butyrylamino)propanoate; and
  • F) other active compounds selected from sulfur-containing heterocyclyl compounds: dithianon; organophosphorus compounds: fosetyl, fosetyl-aluminum, phosphorous acid and its salts; organochlorine compounds: chlorothalonil, thiophanate-methyl; inorganic active compounds: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate; others: cymoxanil, metrafenone; growth retardants: prohexadione and its salts.
  • Preferred embodiments relate to the compositions listed in table B, where in each case one row of table B corresponds to a pesticidal composition comprising the particular compound of the formula I mentioned (component 1 ) and one active compound of the groups mentioned, this active compound preferably being selected from the preferred embodiments defined above.
  • Table B
  • the mixtures according to the invention, or the compound I and the active compound II can be converted into customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • customary formulations for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, for example by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants.
  • Solvents/auxiliaries which are suitable are essentially: water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethyl- amides, fatty acids and fatty acid esters.
  • aromatic solvents for example Solvesso products, xylene
  • paraffins for example mineral oil fractions
  • alcohols for example methanol, butanol, pentanol, benzyl alcohol
  • ketones for example cyclohexan
  • solvent mixtures may also be used, carriers such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethyl- ene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.
  • ground natural minerals for example kaolins, clays, talc, chalk
  • ground synthetic minerals for example highly disperse silica, silicates
  • emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethyl- ene fatty alcohol ethers, alkylsulfonates and arylsulfonates)
  • dispersants such as lignosulfite waste liquors and methylcellulose.
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of ligno- sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octyl- phenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol poly- glycol ethers, tributy
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydro- naphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydro- naphthalene, alkylated naphthalenes or
  • anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
  • Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
  • Suitable preservatives are for example Dichlorophen und enzylalkoholhemiformal.
  • Seed Treatment formulations may additionally comprise binders and optionally colorants.
  • Binders can be added to improve the adhesion of the active materials on the seeds after treatment.
  • Suitable binders are block copolymers EO/PO surfactants but also polyvinyl- alcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyiso- utylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, tylose and copolymers derived from these polymers.
  • colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are 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 1 12, 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 of a gelling agent is carrageen (Satiagel ® ).
  • Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds 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, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth
  • the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound.
  • the active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.
  • a Water-soluble concentrates (SL, LS)
  • the active compounds 20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.
  • the active compound content is 20% by weight.
  • Emulsifiable concentrates 15 parts by weight of the active compounds are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion.
  • the formulation has an active compound content of 15% by weight.
  • the active compounds 25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • This mixture is added into 30 parts by weight of water by means of an emulsifying machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • the formulation has an active compound content of 25% by weight.
  • the active compounds are comminuted with addition of 10 parts by weight of dispersants and wetters and 70 parts by weight of water or an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound.
  • the active compound content in the formulation is 20% by weight.
  • 50 parts by weight of the active compounds are ground finely with addition of 50 parts by weight of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound.
  • the formulation has an active compound content of 50% by weight.
  • Water-dispersible powders and water-soluble powders 75 parts by weight of the active compounds are ground in a rotor- stator mill with addition of 25 parts by weight of dispersants and wetters as well as silica gel. Dilution with water gives a stable dispersion or solution of the active compound.
  • the active compound content of the formulation is 75% by weight.
  • 0.5 part by weight of the active compounds is ground finely and associated with 99.5 parts by weight of carriers.
  • Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active compound content of 0.5% by weight.
  • LS water-soluble concentrates
  • FS suspensions
  • DS dustable powders
  • WS water-dispersible and water-soluble powders
  • ES emulsions
  • EC emulsifiable concentrates
  • gel formulations GF
  • a FS formulation is used for seed treatment.
  • a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring.
  • the use forms depend entirely on the intended purposes; the intention is to ensure in each case the finest possible distribution of the active compounds according to the invention.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • the substances can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • a wetter, tackifier, dispersant or emulsifier it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
  • the active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %.
  • the active compounds may also be used successfully in the ultra-low-volume process (ULV), by which it is possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.
  • UUV ultra-low-volume process
  • oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds, if appropriate not until immediately prior to use (tank mix).
  • These agents can be admixed with the agents according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • compositions of this invention may also contain other active ingredients, for example other pesticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners.
  • additional ingredients may be used sequentially or in combination with the above- described compositions, if appropriate also added only immediately prior to use (tank mix).
  • the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
  • the mixtures of a compound I and a compound Il or the simultaneous, that is joint or separate, use of a compound I and a compound Il are distinguished by being highly active against a wide range of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Peronosporomycetes and Basidiomycetes. Some of them act systemically and can be used in crop protection as foliar fungicides, as fungicides for seed dressing and as soil-acting fungicides.
  • fungi are particularly important for controlling a multitude of fungi on various cultivated plants, such as bananas, cotton, vegetable species (for example cucumbers, beans and cucurbits), barley, grass, oats, coffee, potatoes, corn, fruit species, rice, rye, soya, tomatoes, grapevines, wheat, ornamental plants, sugar cane and also on a large num- ber of seeds.
  • bananas, cotton, vegetables for example cucumbers, beans and cucurbits
  • Albugo spp. white rust
  • vegetables e. g. A. Candida
  • 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,
  • Bipolaris and Drechslera spp. (Teleomorph: Cochliobolus spp.) on corn (e. g. D. may- dis), cereals (e. g. B. sorokiniana: spot blotch), rice (e. g. B. oryzae) and turfs,
  • Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries
  • strawberries e. g. strawberries
  • vegetables e. g. lettuce, carrots, celery and cabbages
  • rape flowers, vines, forestry plants and wheat
  • Bremia lactucae downy mildew
  • Ceratocystis syn. Ophiostoma
  • spp. rot or wilt
  • C. ulmi Dutch elm disease
  • Cercospora spp. (Cercospora leaf spots) on corn, rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice,
  • Cladosporium spp. on tomatoes e. g. C. fulvum: leaf mold
  • cereals e. g. C. herba- rum (black ear) on wheat
  • 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. (anthracnose) on cotton (e. g. C. gos- sypii), corn (e. g. C. graminicola), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum),
  • Corticium spp. e. g. C. sasakii (sheath blight) on rice
  • Corynespora cassiicola (leaf spots) on soybeans and ornamentals
  • Cycloconium spp. e. g. C. oleaginum on olive trees
  • Cylindrocarpon spp. e. g. fruit tree canker or young vine decline
  • teleomorph Nectria or Neonectria spp.
  • vines e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease
  • Dematophora teleomorph: Rosellinia necatrix (root and stem rot) on soybeans
  • Diaporthe spp. e. g. D. phaseolorum (damping off) on soybeans
  • Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf,
  • Esca dieback, apoplexy on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamy- dosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa,
  • Elsinoe spp. on pome fruits E. pyri
  • soft fruits E. veneta: anthracnose
  • vines E. ampelina: anthracnose
  • Entyloma oryzae (leaf smut) on rice
  • Epicoccum spp. black mold
  • 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),
  • E. betae sugar beets
  • vegetables e. g. E. pisi
  • 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),
  • Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice,
  • Hemileia spp. e. g. Hemileia vastatrix (coffee leaf rust) on coffee, lsariopsis clavispora (syn. Cladosporium vitis) on vines,
  • 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
  • Peronospora spp. downy mildew on cabbage (e. g. P. brassicae), rape (e. g. P. para- sitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica),
  • P. gregata stem rot
  • Phoma lingam root and stem rot
  • rape and cabbage rape and cabbage
  • P. betae root rot, leaf spot and damping-off
  • stem rot P. phaseoli
  • teleomorph Diaporthe phaseolorum
  • Physorma maydis brown spots
  • 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)
  • 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. ramorum: sudden oak death
  • 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 rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples,
  • Polymyxa spp. e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases,
  • Pseudoperonospora downy mildew
  • various plants e. g. P. cubensis on cucurbits or P. humili on hop
  • Pseudopezicula tracheiphila red fire disease or , rotbrenner' , anamorph: Phialophora
  • Puccinia spp. rusts on various plants, e. g. P. triticina (brown or leaf rust), P. stri- iformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or
  • Pyrenophora anamorph: Drechslera
  • tritici-repentis tan spot
  • P. teres net blotch
  • 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, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum), Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets ,
  • Rhizopus stolonifer black mold, soft rot on strawberries, carrots, cabbage, vines and tomatoes
  • 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),
  • Septoria spp. on various plants e. g. S. glycines (brown spot) on soybeans, S. tritici
  • 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 e. g. S. reiliana: head smut
  • Stagonospora spp. on cereals e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat,
  • T. deformans leaf curl disease
  • T. pruni plum pocket
  • Thielaviopsis spp. black root rot
  • tobacco, pome fruits, vegetables, soybeans and cotton e. g. T. basicola (syn. Chalara elegans)
  • Tilletia spp. common bunt or stinking smut
  • cereals such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat,
  • Urocystis 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)
  • beans e. g. U. appendiculatus, syn. U. phaseoli
  • sugar beets e. g. U. betae
  • Ustilago spp. loose smut on cereals (e. g. U. nuda und U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane,
  • Venturia spp. scab
  • apples e. g. V. inaequalis
  • pears Verticillium spp.
  • 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 of the compounds I and active compounds Il are furthermore suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
  • harmful fungi Ascomycetes, such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes, such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Tyromyces spp. Deuteromycetes, such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes, such as Mucor spp., additionally in the protection of materials the following yeasts: Candida spp. and Saccharomyces cerevisae.
  • the compounds I and the one or more compound(s) Il are usually applied in a weight ratio of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 20:1 to 1 :20, in particular from 10:1 to 1 :10.
  • the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 1500 g/ha, in particular from 50 to 750 g/ha.
  • mixtures of a compound I with an active compound Il are employed.
  • mixtures of the compound I with two or, if appropriate, more active components may be advantageous.
  • Suitable further active components in the above sense are in particluar the active compounds II, mentioned at the outset and in particular the preferred active compounds mentioned above.
  • the mixtures of the compounds I and active compounds Il are employed by treating the fungi or the plants, seeds, materials or soil to be protected from fungal attack with a fungicidally effective amount of the active compounds.
  • the application can be carried out both before and after the infection of the materials, plants or seeds by the fungi.
  • the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 900 g/ha, in particular from 50 to 750 g/ha.
  • the application rates for the compound I are generally from 1 to 1000 g/ha, preferably from 10 to 900 g/ha, in particular from 20 to 750 g/ha.
  • the application rates for the active compound Il are generally from 1 to 2000 g/ha, preferably from 10 to 900 g/ha, in particular from 40 to 500 g/ha.
  • the method for controlling harmful fungi is carried out by the separate or joint applica- tion of a compound I and the active compound Il or the mixtures of the compound I and the active compound Il by spraying or dusting the seeds, the plants or the soil before or after sowing of the plants or before or after emergence of the plants.
  • the treatment can be made into the seedbox before planting into the field.
  • the compounds I and Il or the mixtures or the corresponding formulations are applied by treating the harmful fungi, the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally effective amount of the mixture or, in the case of separate application, of the compounds I and II.
  • Application can be carried out before or after infection by the harmful fungi.
  • insects from the order of the lepidopterans for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou- liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo- lesta, Heli
  • beetles Coldoptera
  • Agrilus sinuatus for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blasto- phagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabro
  • mosquitoes e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, An- astrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis,
  • thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp , Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
  • Isoptera e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Re- ticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus,
  • cockroaches e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
  • Hemiptera true bugs
  • Hoplocampa minuta Hoplocampa testudinea, Lasius niger, Mo- nomorium pharaonis, Sol
  • Vespula squamosa Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula macula- ta, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile,
  • crickets grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllo- talpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina,
  • Arachnoidea such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodo- rus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyss
  • Aculus e.g. Aculus
  • Phyllocoptrata oleivora and Eriophyes sheldoni Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus
  • Tenuipalpidae spp. such as Brevipalpus phoenicis
  • Tetra- nychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panony- chus citri, and Oligonychus pratensis
  • Araneida e.g. Latrodectus mactans, and Loxos- celes reclusa
  • Latrodectus mactans e.g. Latrodectus mactans, and Loxos- cele
  • fleas e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
  • silverfish, firebrat e.g. Lepisma saccharina and Thermobia domestica
  • centipedes Chilopoda
  • Scutigera coleoptrata centipedes
  • millipedes e.g. Narceus spp.
  • Earwigs e.g. forficula auricularia
  • Pediculus humanus capitis e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthi- rus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus,
  • plant parasitic nematodes such as root-knot nematodes, Meloidogyne arenaria, Meloi- dogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica and other Meloidogyne species; cyst nematodes, Globodera rostochiensis, Globodera pallida, Globodera tabacum and other Globodera species, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; seed gall nematodes, Anguina funesta, Anguina tritici and other Anguina species; stem and foliar nematodes, Aphelenchoides besseyi, Aphelen- choides fragariae, Aphelen
  • inventive mixtures are especially useful for the control of non-crop pests (household, turf, ornamental).
  • the mixtures according to the invention can be applied to any and all developmental stages of pests, such as egg, larva, pupa, and adult.
  • the pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the inventive mixtures or of compositions comprising the mixtures.
  • Locus means a plant, seed, soil, area, material or environment in which a pest is growing or may grow.
  • pesticidally effective amount means the amount of the inventive mixtures or of compositions comprising the mixtures needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various mixtures / compositions used in the invention.
  • a pesticidally effective amount of the mixtures / compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • inventive mixtures or compositions of these mixtures can also be employed for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting a plant, or soil or water in which the plant is growing.
  • the term plant refers to an entire plant, a part of the plant or the propagation material of the plant, that is, the seed or the seedling.
  • Plants which can be treated with the inventive mixtures include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures.
  • seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • the compounds I and the one or more compound(s) Il can be applied simultaneously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
  • inventive mixtures are also suitable for the protection of the seed and the seedlings' roots and shoots, preferably the seeds, against soil pests.
  • compositions which are especially useful for seed treatment are e.g.:
  • a Soluble concentrates (SL, LS) D Emulsions (EW, EO, ES) E Suspensions (SC, OD, FS)
  • Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. Preferred are FS formulations.
  • the application rates of the inventive mixture are generally from 0.001 to 10 kg per 100 kg of seed, dependent from the desired effect and the kind of seed. Application rates are preferably from 1 to 1000 g/100 kg of seed, more preferably from 1 to 750 g/100 kg, in particular from 5 to 500 g/100 kg.
  • the separate or joint application of the compounds I and Il or of the mixtures of the compounds I and Il is carried out by spraying or dusting the seeds, the seedlings, the plants or the soils before or after sowing of the plants or before or after emergence of the plants.
  • the invention also relates to the propagation products of plants, and especially the seed comprising, that is, coated with and/or containing, a mixture as defined above or a composition containing the mixture of two or more active ingredients or a mixture of two or more compositions each providing one of the active ingredients.
  • the seed com- prises the inventive mixtures in an amount of from 0.1 g to 10 kg per 100 kg of seed.
  • the inventive mixtures are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part) and through trophallaxis and transfer.
  • Preferred application methods are into water bodies, via soil, cracks and crevices, pastures, manure piles, sewers, into water, on floor, wall, or by perimeter spray application and bait.
  • the inventive mixtures are prepared into a bait preparation.
  • the bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
  • the bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it.
  • This attractant may be chosen from feeding stimulants or para and / or sex phero- mones readily known in the art.
  • Methods to control infectious diseases transmitted by insects with the inventive mixtures and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like, lnsecticidal compositions for application to fibers, fabric, knitgoods, non- wovens, netting material or foils and tarpaulins preferably comprise a composition in- eluding the inventive mixtures, optionally a repellent and at least one binder.
  • inventive mixtures and the compositions comprising them can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 2O g per 100 m 2 .
  • Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .
  • lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and / or insecticide.
  • the typical content of active ingredient is from 0.0001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
  • the composition used may also comprise other additives such as a solvent of the active material, a flavoring agent, a preserving agent, a dye or a bitter agent. Its attractiveness may also be enhanced by a special color, shape or texture.
  • the content of the mixture of the active ingredients is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
  • the rate of application of the mixture of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
  • This invention also provides a method for treating, controlling, preventing and protecting warm-blooded animals, including humans, and fish against infestation and infection by pests of the orders Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera, and Diptera, which comprises orally, topically or parenterally administering or applying to said animals a pesticidally effective amount of mixtures according to the invention.
  • the invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting a warm-blooded animal or a fish against infestation or infection by pests of the Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera, and Diptera orders which comprises a pesticidally effective amount of a mixture according to the invention.
  • the above method is particularly useful for controlling and preventing infestations and infections in warm-blooded animals such as cattle, sheep, swine, camels, deer, horses, poultry, goats, dogs and cats as well as humans.
  • Infestations in warm-blooded animals and fish including, but not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas may be controlled, prevented or eliminated by the mixtures according to the invention.
  • the mixtures according to the invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules.
  • the mixtures according to the invention may be administered to the animals in their drinking water.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the mixture.
  • the mixtures according to the invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
  • the mixtures according to the invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection.
  • the mixtures according to the invention may be formulated into an implant for subcutaneous administration.
  • the mixtures according to the invention may be transdermally administered to animals.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the mixture.
  • the mixtures according to the invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, spot-on and pour-on for- mulations.
  • dips and sprays usually contain 0.5 ppm to 5000 ppm and preferably 1 ppm to 3000 ppm of the inventive compounds.
  • the mixtures according to the invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the products pyraclostrobin, benthivali- carb, fenhexamid, boscalid and metlaxyl-M were used as commercial finished formulations and diluted with water to the stated concentration of the active compound.
  • 1-2 corresponds to the compound of formula 1-2, i.e. N-Ethyl-2,2-dichloro-1- methylcyclopropane-carboxamide-2-(2,6-dichloro- ⁇ , ⁇ , ⁇ -trifluoro-p-tolyl)hydrazone, as described hereinabove.
  • the stock solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the stated concentrations.
  • MTP microtiter plate
  • 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 infection level of the treated variant corresponds to that of the active compound-free control plants; an efficacy of 100 means that the treated variants are not infected.
  • E expected efficacy expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b; x efficacy, expressed in % of the untreated control, when using the active compound A at the concentration a; y efficacy, expressed in % of the untreated control, when using the active compound B at the concentration b.
  • Table Vl Activity against Gibberella Zeae (Gibbze)
  • Table VII Activity against Monographella nivalis (Mongni)
  • Table XV Activity against Colleotrichum truncatum
  • Table XX Activity against Fusarium culmorum (Fusacu)

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Abstract

Pesticidal mixtures comprising, as active components, 1)an amidrazone of the formula (I): wherein the substituents are as defined in the description, and 2)at least one fungicidal compound II selected from the following groups: azoles, strobilurins, carboxamides, heterocylic compounds, carbamates, guanidi- nes, antibiotics, nitrophenyl derivates, sulfur-containing heterocyclyl compounds, organometal compounds, organophosphorus compounds, organochlorine compounds, inorganic active compounds, and cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone and spiroxamine; in a synergistically effective amount, methods for controlling pests, and harmful fungi, methods of protecting plants from attack or infestation by insects, acarids or nema- todes, compositions containing these mixtures, and methods for their preparation.

Description

Pesticidal mixtures Description The present invention relates to pesticidal mixtures comprising, as active components, 1 ) an amidrazone of the formula I
Figure imgf000002_0001
wherein
R is hydrogen, d-Cβ-alkyl, d-Cβ-alkoxycarbonyl, d-Cβ-alkylaminocarbonyl, or di(Ci-C6-alkyl)-aminocarbonyl,
wherein in each of the above radicals the alkyl group is unsubstituted or substituted with 1 to 3 substituents independently selected from halogen, cyano, nitro, d-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkoxy, d-Cβ-alkylthio, d-Ce-haloalkylthio, d-Ce-alkylsulfonyl, Ci-C6-alkylsulfinyl, and di(Ci-C6alkyl)-amino;
R1 and R2 are each independently hydrogen, Ci-Cio-alkyl, C3-Cio-alkenyl,
C3-Cio-alkynyl, C3-Ci2-cycloalkyl, Ci-Cε-alkylamino, di(d-Ce-alkyl)- amino, Ci-Cβ-alkylcarbonylamino, Ci-Cβ-alkylsulfonyl, or
Figure imgf000002_0002
wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups are unsubstituted or substituted with 1 to 3 substituents independently selected from halogen, nitro, cyano, d-Cβ-alkoxy, C-i-Cβ-haloalkoxy, C-i-Cε-alkylthio, d-Ce-haloalkylthio, d-Ce-alkylsulfonyl, d-Ce-alkylsulfinyl, Ci-Cβ-haloalkylsulfonyl, Ci-C6-haloalkylsulfinyl, C3-C6-cycloalkyl, phenyl, and pyridyl;
R3 is d-do-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, C3-Ci2-cycloalkyl, wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups are unsubstituted or partially or fully halogenated and/or substituted with
1 to 3 substituents independently selected from cyano, nitro, hydroxy, mercapto, amino, Ci-Cβ-alkyl, Cs-Cβ-cycloalkyl, d-Cβ-alkoxy, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)-amino, C-i-Cε-alkylthio, Ci-Cβ-alkylsulfonyl, and Ci-Cβ-alkylsulfinyl, or
a 3- to 6-membered saturated or partially unsaturated ring which may contain 1 to 3 heteroatoms selected from oxygen, sulfur and nitrogen, and which is unsubstituted or substituted with 1 to 5 substituents independently selected from halogen, Ci-Cβ-alkyl, C-i-Cβ-alkylthio, Ci-Cβ-alkylsulfonyl, Ci-Cβ-alkylsulfinyl, Ci-Cβ-alkoxy, C-i-Cβ-haloalkoxy, nitro and cyano, wherein in each of the above radicals the alkyl group is unsubstituted or substituted with 1 to 3 halogen atoms;
A is C-R4 or N;
B is C-R5 Or N; W is C-R6 or N;
with the proviso that one of A, B and W is other than N;
R4, R5, R6 are each independently hydrogen, halogen, nitro, cyano, amino, mercapto, hydroxy, Ci-Cio-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl,
C3-C6-cycloalkyl, Ci-Cβ-alkoxy, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)- amino, C-i-Cβ-alkylthio, Ci-Cβ-alkylsulfonyl, Ci-Cβ-alkylsulfinyl, or a 5- to 6-membered aromatic ring which may contain 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen;
Y is hydrogen, halogen, cyano, nitro, amino, hydroxy, mercapto, Ci-Cβ-alkyl,
C2-Cio-alkenyl, C2-Cio-alkynyl, Cs-Cβ-cycloalkyl, Ci-Cβ-alkoxy, Ci-Cβ-alkylamino, di(Ci-C6)-alkylamino, C-i-Cβ-alkylthio, Ci-Cβ-alkylsulfonyl, or Ci-Cβ-alkylsulfinyl; and
n is O, 1 , or 2;
and
2) at least one fungicidal compound Il selected from the following groups: A) azoles, in particular: bitertanol, bromuconazole, cyproconazole, difeno- conazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fen- buconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipcona- zole, metconazole, myclobutanil, penconazole, propiconazole, prothiocona- zole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole; prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid; benomyl, carbendazim, thiabendazole, fuberidazole; ethaboxam, etridiazole, hymexazole;
B) strobilurins, in particular: azoxystrobin, dimoxystrobin, enestroburin, fluoxa- strobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, or methyl (2-chloro-5-[1-(3-methylbenzyloxy- imino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1 -(6-methylpyridin-2-yl- methoxyimino)ethyl]benzyl)carbamate, methyl 2-(ortho-((2,5-dimethylphe- nyloxymethylene)phenyl)-3-methoxyacrylate;
C) carboxamides, in particular: carboxin, benalaxyl, boscalid, fenhexamid, flu- tolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, N-(4'-bromobiphenyl-2-yl)-
4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4'-trifluoromethylbi- phenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4'-chloro- 3'-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(3',4'-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4- carboxamide, N-(3',4'-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1 - methylpyrazole-4-carboxamide;
3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide; dimethomorph, flumorph; flumetover, fluopicolide (picobenzamid), zoxamide; carpropamid, diclocymet, mandipropamid;
N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2- methanesulfonylamino-3-methylbutyramide, N-(2-{4-[3-(4-chlorophenyl)- prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethanesulfonylamino-3-methyl- butyramide;
D) heterocylic compounds, in particular: fluazinam, pyrifenox; bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil; triforine; fenpiclonil, fludioxonil; aldimorph, dodemorph, fenpropimorph, tridemorph; fenpropidin, iprodione, procymidone, vinclozolin; famoxadone, fenamidone, octhilinone, probenazole; amisulbrom, anilazine, diclomezine, pyroquilon, proquinazid, tricyclazole; 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine,
2-butoxy-6-iodo-3-propylchromen-4-one; acibenzolar-S-methyl, captafol, captan, dazomet, folpet, fenoxanil, quin- oxyfen; 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine;
E) carbamates, in particular: mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram; benthiavalicarb, diethofencarb, iprovalicarb, flubenthiavalicarb, propamocarb; methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methyl- butyrylamino)propanoate; and F) other active compounds, selected from guanidines: dodine, iminoctadine, guazatine; antibiotics: kasugamycin, streptomycin, polyoxine, validamycin A; nitrophenyl derivates: binapacryl, dinocap, dinobuton; sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane; organometal compounds: fentin salts, such as fentin-acetate; organophosphorus compounds: edifenphos, iprobenfos, fosetyl, fosetyl- aluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; organochlorine compounds: chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate- methyl, tolylfluanid; inorganic active compounds: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; others: cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone and spiroxamine
in a synergistically effective amount.
Moreover, the invention relates to a method for controlling pests, using mixtures of a compound I with active compounds Il and to the use of the compounds I with the active compounds Il for preparing such mixtures, and also to compositions comprising such mixtures.
As used herein, the term "pest" is considered to include any harmful organisms including insects, acarids, nematodes, and phytopathogenic fungi. Thus, the invention relates to a method for controlling phytopathogenic harmful fungi using mixtures of a compound I with active compounds Il and to the use of a compound I with active compounds Il for preparing such mixtures, and also to compositions com- prising these mixtures.
In one embodiment, the present invention provides methods for the control of insects, acarids or nematodes comprising contacting the insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with a pesticidally effective amount of mixtures of a compound I with one or more compounds II.
In another embodiment, the present invention also relates to a method of protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or the soil or water in which the plant is growing, with a pesticidally effec- tive amount of a mixture of a compound I with one or more compounds 11.
This invention also provides a method for treating, controlling, preventing or protecting a warm-blooded animal or fish against infestation or infection by insects, acarids or nematodes which comprises orally, topically or parenterally administering or applying to the animal or fish a pesticidally effective amount of a mixture of a compound I with one or more compounds II.
The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting a warm-blooded animal or a fish against infestation or infection by insects, acarids or nematodes which comprises a pesticidally effective amount of a mixture of a compound I with one or more compounds II.
The amidrazones of formula I referred to above as component 1 , their preparation and their action against insect and acarid pests are known (cf. for example, EP-A 604 798, J. A. Furch et al., "Amidrazones: A New Class of Coleopteran Insecticides", ACS Symposium Series 686, Am. Chem. Soc, 1998, Chapter 18, pp. 178; and D. G. Kuhn et al., "Cycloalkyl-substituted Amidrazones: A Novel Class of Insect Control Agents", ACS Symposium Series 686, Am. Chem. Soc, 1998, Chapter 19, pp. 185). The amidrazones of formula I can be obtained by the preparation methods as described or refer- enced in EP-A 604 798. Moreover, an alternative route for their preparation is disclosed in co-pending European patent application No. 06118365.3 filed on August 3, 2006.
WO 2006/128863 A1 discloses mixtures of the amidrazones of formula I with certain insecticides. In general, mixtures of the amidrazones I with a fungicide, and their favourable synergistic effect are not known from the prior art.
The active compounds Il mentioned above as component 2, their preparation and their action against harmful fungi are generally known (cf.: http://www.hclrss.demon.co.uk/index.html); they are commercially available. Paticu- larly, they are known from: bitertanol, β-([1 ,1 '-biphenyl]-4-yloxy)-α-(1 ,1-dimethylethyl)- 1 H-1 ,2,4-triazole-1-ethanol (DE 23 24 020), bromuconazole, 1-[[4-bromo-2-(2,4-di- chlorophenyl)tetrahydro-2-furanyl]methyl]-1 H-1 ,2,4-triazole (Proc. 1990 Br. Crop. Prot. Conf. - Pests Dis. Vol. 1 , p. 459); cyproconazole, 2-(4-chlorophenyl)-3-cyclopropyl-1- [1 ,2,4]triazol-1-ylbutan-2-ol (US 4 664 696); difenoconazole, 1-{2-[2-chloro-4-(4-chloro- phenoxy)phenyl]-4-methyl-[1 ,3]dioxolan-2-ylmethyl}-1 H-[1 ,2,4]triazole (GB-A 2 098 607); diniconazole, (βE)-β-[(2,4-dichlorophenyl)methylene]-α-(1 ,1-dimethylethyl)-1 H- 1 ,2,4-triazole-1-ethanol (Noyaku Kagaku, 1983, Vol. 8, p. 575); enilconazole (imazalil), 1 -[2-(2,4-dichlorphenyl)-2-(2-propenyloxy)ethyl]-1 H-imidazole (Fruits, 1973, Vol. 28, p. 545); epoxiconazole, (2RS,3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophe- nyl)propyl]-1 H-1 ,2,4-triazole (EP-A 196 038); fluquinconazole, 3-(2,4-dichlorophenyl)-6- fluoro-2-[1 ,2,4]-triazol-1-yl-3H-quinazolin-4-one (Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 41 1 (1992)); fenbuconazole, α-[2-(4-chlorophenyl)ethyl]-α-phenyl-1 H-1 ,2,4-tri- azole-1-propanenitrile (Proc. 1988 Br. Crop Prot. Conf. - Pests Dis. Vol. 1 , p. 33); flusi- lazole, 1-{[bis-(4-fluorophenyl)methylsilanyl]methyl}-1 H-[1 ,2,4]triazole (Proc. Br. Crop Prot. Conf.-Pests Dis., 1 , 413 (1984)); flutriafol, α-(2-fluorophenyl)-α-(4-fluorophenyl)- 1 H-1 ,2,4-triazole-1-ethanol (EP 15 756); hexaconazole, 2-(2,4-dichlorophenyl)-1- [1 ,2,4]triazol-1-ylhexan-2-ol (CAS RN 79983-71-4); imibenconazole, (4-chlorophe- nyl)methyl N-(2,4-dichlorophenyl)-1 H-1 ,2,4-triazole-1 -ethanimidothioate ((Proc. 1988 Br. Crop Prot. Conf. - Pests Dis. Vol. 2, p. 519); imidothioate ((Proc. 1988 Br. Crop Prot. Conf. - Pests Dis. Vol. 2, p. 519); ipconazole, 2-[(4-chlorophenyl)methyl]-5-(1- methylethyl)-1-(1 H-1 ,2,4-triazol-1-ylmethyl)cyclopentanol (EP 267 778); metconazole, 5-(4-chlorobenzyl)-2,2-dimethyl-1-[1 ,2,4]triazol-1-ylmethylcyclopentanol (GB 857 383); myclobutanil, 2-(4-chlorophenyl)-2-[1 ,2,4]triazol-1-ylmethylpentanenitrile (CAS RN 88671-89-0); penconazole, 1-[2-(2,4-dichlorophenyl)pentyl]-1 H-[1 ,2,4]triazole (Pesticide Manual, 12th Ed. (2000), p.712); propiconazole, 1-[[2-(2,4-dichlorophenyl)-4- propyl-1 ,3-dioxolan-2-yl]methyl]-1 H-1 ,2,4-triazole (BE 835 579); prothioconazole, 2-[2- (1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1 ,2,4]triazole-3- thione (WO 96/16048); simeconazole, α-(4-fluorophenyl)-α-[(trimethylsilyl)methyl]-1 H- 1 ,2,4-triazole-1-ethanol [CAS RN 149508-90-7] ; triadimefon, 1-(4-chlorophenoxy)-3,3- dimethyl-1-(1 H-1 ,2,4-triazol-1-yl)-2-butanone; triadimenol, β-(4-chlorophenoxy)-α-(1 ,1- dimethylethyl)-1 H-1 ,2,4-triazole-1-ethanol; tebuconazole, 1-(4-chlorophenyl)-4,4-di- methyl-3-[1 ,2,4]triazol-1-ylmethylpentan-3-ol (EP-A 40 345); tetraconazole, 1-[2-(2,4- dichlorophenyl)-3-(1 ,1 ,2,2-tetrafluoroethoxy)propyl]-1 H-1 ,2,4-triazole (EP 234 242); triticonazole, (5E)-5-[(4-chlorophenyl)methylene]-2,2-dimethyl-1 -(1 H-1 ,2,4-triazol-1 - ylmethyl)cyclopentanol (FR 26 41 277); prochloraz, N-{propyl-[2-(2,4,6-trichlorophen- oxy)ethyl]}imidazole-1-carboxamide (US 3 991 071 ); pefurazoate, 4-pentenyl 2-[(2-fu- ranylmethyl)(1 H-imidazol-1-ylcarbonyl)amino]butanoate [CAS RN 101903-30-4] ; tri- flumizole, (4-chloro-2-trifluoromethylphenyl)-(2-propoxy-1 -[1 ,2,4]triazol-1 -ylethyli- dene)amine (JP-A 79/119 462); cyazofamid, 4-chloro-2-cyano-N,N-dimethyl-5-(4-me- thylphenyl)-1 H-imidazole-1 -sulfonamide (CAS RN 120116-88-3]; benomyl, N-butyl-2- acetylaminobenzoimidazol-1-carboxamide (US 3 631 176); carbendazim, methyl (1 H- benzoimidazol-2-yl)-carbamate (US 3 657 443); thiabendazole, 2-(1 ,3-thiazol-4- yl)benzimidazole (US 3 017 415) ; fuberidazole, 2-(2-furanyl)-1 H-benzimidazole (DE 12 09 799); ethaboxam, N-(cyano-2-thienylmethyl)-4-ethyl-2-(ethylamino)-5-thiazolcarbox- amide (EP-A 639 574); etridiazole; hymexazole, 5-methyl-1 ,2-oxazol-3-ol (JP 518249, JP 532202); azoxystrobin, methyl 2-{2-[6-(2-cyano-1-vinylpenta-1 ,3-dienyloxy)pyrimi- din-4-yloxy]phenyl}-3-methoxyacrylate (EP-A 382 375); dimoxystrobin, (E)-2-(methoxy- imino)-N-methyl-2-[α-(2,5-xylyloxy)-o-tolyl]acetamide (EP-A 477 631 ); fluoxastrobin, (E)-{2-[6-(2-chlorophenoxy)-5-fluoropyrimidin-4-yloxy]phenyl}(5,6-dihydro-1 ,4,2-dioxa- zin-3-yl)methanone O-methyloxime (WO 97/27189); kresoxim-methyl, methyl (E)-me- thoxyimino[α-(o-tolyloxy)-o-tolyl]acetate (EP-A 253 213); metominostrobin, (E)-2-(me- thoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide (EP-A 398 692); orysastrobin, (2E)-2-(methoxyimino)-2-{2-[(3E,5E,6E)-5-(methoxyimino)-4,6-dimethyl-2,8-dioxa-3,7- diazanona-3,6-dien-1-yl]phenyl}-N-methylacetamide (WO 97/15552); picoxystrobin, methyl 3-methoxy-2-[2-(6-trifluoromethylpyridin-2-yloxymethyl)phenyl]acrylate (EP-A 278 595); pyraclostrobin, methyl N-{2-[1-(4-chlorophenyl)-1 H-pyrazol-3-yloxyme- thyl]phenyl}(N-methoxy)carbamate (WO-A 96/01256); trifloxystrobin, methyl (E)-me- thoxyimino-{(E)-α-[1-(α,α,α-trifluoro-m-tolyl)ethylideneaminooxy]-o-tolyl}acetate (EP-A 460 575); carboxin, 5,6-dihydro-2-methyl-N-phenyl-1 ,4-oxathiin-3-carboxamide (US 3 249 499); benalaxyl, methyl N-(phenylacetyl)-N-(2,6-xylyl)-DL-alaninate (DE 29 03 612); boscalid, 2-chloro-N-(4'-chlorbiphenyl-2-yl)nicotinamide (EP-A 545 099); fen- hexamid, N-(2,3-dichloro-4-hydroxyphenyl)-1-methylcyclohexanecarboxamide (Proc. Br. Crop Prot. Conf. - Pests Dis., 1998, Vol. 2, p. 327); flutolanil,α,α,α-trifluoro-3'- isopropoxy-o-toluanilide (JP 1104514); furametpyr, 5-chloro-N-(1 ,3-dihydro-1 ,1 ,3- trimethyl-4-isobenzofuranyl)-1 ,3-dimethyl-1 H-pyrazole-4-carboxamide [CAS RN 123572-88-3]; mepronil, 3'-isopropoxy-o-toluanilide (US 3 937 840); metalaxyl, methyl N-(methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate (GB 15 00 581); mefenoxam, methyl N- (2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate; ofurace, (RS)-α-(2-chloro-N-2,6- xylylacetamido)-γ -butyrolactone [CAS RN 58810-48-3]; oxadixyl; N-(2,6-dimethyl- phenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)acetamide (GB 20 58 059); oxycarboxin, 5,6-dihydro-2-methyl-1 ,4-oxathiin-3-carboxanilide 4,4-dioxide (US 3 399 214); pen- thiopyrad, N-[2-(1 ,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1 H-pyrazole- 4-carboxamide (JP 10130268); thifluzamide, N-[2,6-dibromo-4-(trifluorometh- oxy)phenyl]-2-methyl-4-(trifluoromethyl)-5-thiazolecarboxamide; tiadinil, 3'-chloro-4,4'- dimethyl-1 ,2,3-thiadiazole-5-carboxanilide [CAS RN 223580-51-6]; dimethomorph, 3- (4-chlorophenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-ylpropenone (EP-A 120 321 ); flumorph, 3-(4-fluorophenyl)-3-(3,4-dimethoxyphenyl)-1 -morpholin-4-ylpropenone (EP- A 860 438); flumetover, 2-(3,4-dimethoxyphenyl)-N-ethyl-α,α,α-trifluoro-N-methyl-p- toluamide [AGROW No. 243, 22 (1995)]; fluopicolide (picobenzamid), 2,6-dichloro-N- (3-chloro-5-trifluoromethylpyridin-2-ylmethyl)benzamide (WO 99/42447); zoxamide, (RS)-3,5-dichloro-N-(3-chloro-1 -ethyl-1 -methyl-2-oxopropyl)-p-toluamide [CAS RN 156052-68-5]; carpropamid, 2,2-dichloro-N-[1 -(4-chlorophenyl)ethyl]-1 -ethyl-3-methyl- cyclopropanecarboxamide [CAS RN 104030-54-8]; diclocymet, 2-cyano-N-[(1 R)-1-(2,4- dichlorophenyl)ethyl]-3,3-dimethyl butanamide; mandipropamid, (RS)-2-(4-chloro- phenyl)-N-[3-methoxy-4-(prop-2-ynyloxy)phenethyl]-2-(prop-2-ynyloxy)acetamide [CAS RN 374726-62-2]; fluazinam, 3-chloro-N-[3-chloro-2,6-dinitro-4-(trifluoromethyl)phenyl]- 5-(trifluoromethyl)-2-pyridinamine (The Pesticide Manual, publ. The British Crop Protection Council, 10th ed. (1995), p. 474); pyrifenox, 1-(2,4-dichlorophenyl)-2-(3-pyridi- nyl)ethanone O-methyloxime (EP-A 49 854); bupirimate, 5-butyl-2-ethylamino-6-methyl- pyrimidin-4-yldimethylsulfamate [CAS RN 41483-43-6]; cyprodinil, (4-cyclopropyl-6- methylpyrimidin-2-yl)phenylamine (EP-A 310 550); fenarimol, (4-chlorophenyl) (2- chlorophenyl) pyrimidin-5-ylmethanol (GB 12 18 623); ferimzone, (Z)-2'-methylaceto- phenone 4,6-dimethylpyrimidin-2-ylhydrazone [CAS RN 89269-64-7]; mepanipyrim, (4- methyl-6-prop-1-ynylpyrimidin-2-yl)phenylamine (EP-A 224 339); nuarimol, α-(2-chloro- phenyl)-α-(4-fluorophenyl)-5-pyrimidinemethanol (GB 12 18 623); pyrimethanil, 4,6-di- methylpyrimidin-2-ylphenylamine (DD-A 151 404); triforine, N,N-{piperazine-1 ,4-diyl- bis[(trichloromethyl)methylene]}diformamide (DE 19 01 421); fenpiclonil, 4-(2,3-di- chlorophenyl)-1 H-pyrrole-3-carbonitrile (Proc. 1988 Br. Crop Prot. Conf. - Pests Dis., Vol. 1 , p. 65); fludioxonil, 4-(2,2-difluorobenzo[1 ,3]dioxol-4-yl)-1 H-pyrrole-3-carbonitrile (The Pesticide Manual, publ. The British Crop Protection Council, 10th ed. (1995), p. 482); aldimorph, 4-alkyl-2,5(or 2,6)-dimethylmorpholine, comprising 65-75% of 2,6-di- methylmorpholine and 25-35% of 2,5-dimethylmorpholine, comprising more than 85% of 4-dodecyl-2,5(or 2,6)-dimethylmorpholine, where "alkyl" may also include octyl, de- cyl, tetradecyl or hexadecyl and where the cis/trans ratio is 1 :1 ; dodemorph, 4-cyclo- dodecyl-2,6-dimethylmorpholine (DE 1 198125); fenpropimorph, (RS)-cis-4-[3-(4-tert- butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine (DE 27 52 096); tridemorph, 2,6- dimethyl-4-tridecylmorpholine (DE 1 1 64 152); fenpropidin, (RS)-I -[3-(4-tert-butylphe- nyl)-2-methylpropyl]piperidine (DE 27 52 096); iprodione, N-isopropyl-3-(3,5-dichloro- phenyl)-2,4-dioxoimidazolidine-1-carboxamide (GB 13 12 536); procymidone, N-(3,5- dichlorophenyl)-1 ,2-dimethylcyclopropane-1 ,2-dicarboximide (US 3 903 090); vinclo- zolin, 3-(3,5-dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione (DE-OS 22 07 576); famoxadone, (RS)-3-anilino-5-methyl-5-(4-phenoxyphenyl)-1 ,3-oxazolidine-2,4-dione; fenamidone, (S)-1 -anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one; octhilinone; probenazole, 3-allyloxy-1 ,2-benzothiazole 1 ,1-dioxide; amisulbrom, N,N-dimethyl-3-(3- bromo-6-fluoro-2-methylindole-1 -sulfonyl)-[1 ,2,4]triazole-1 -sulfonamide (WO
03/053145); anilazine, 4,6-dichloro-N-(2-chlorophenyl)-1 ,3,5-triazine-2-amine (US 2 720 480); diclomezine, 6-(3,5-dichlorophenyl)-p-tolyl)pyridazin-3(2H)-one; pyroquilon; proquinazid, 6-iodo-2-propoxy-3-propylquinazolin-4(3H)-one (WO 97/48684); tricycla- zole, 5-methyl-1 ,2,4-triazolo[3,4-b]benzothiazole (GB 14 19 121 ); acibenzolar-S-me- thyl, methyl benzo[1 ,2,3]thiadiazole-7-carbothionate; captafol, N-(1 ,1 ,2,2-tetrachloro- ethylthio)cyclohex-4-ene-1 ,2-dicarboximide; captan, 2-trichloromethylsulfanyl-
3a,4,7,7a-tetrahydroisoindole-1 ,3-dione (US 2 553 770); dazomet, 3,5-dimethyl-1 ,3,5- thiadiazinane-2-thione; folpet, 2-trichloromethylsulfanylisoindole-1 ,3-dione (US 2 553 770); fenoxanil, N-(1-cyano-1 ,2-dimethylpropyl)-2-(2,4-dichlorophenoxy) propanamide; quinoxyfen, 5,7-dichloro-4-(4-fluorophenoxy)quinoline (US 5 240 940); mancozeb, manganese ethylenebis(dithiocarbanate) zinc complex (US 3 379 610); maneb, manganese ethylenebis(dithiocarbamate) (US 2 504 404); metam, methyldithiocarbaminic acid (US 2 791 605); metiram, zinc ammoniate ethylenebis(dithiocarbamate) (US 3 248 400); propineb, zinc propylenebis(dithiocarbamate) polymer (BE 611 960); ferbam, iron(3+) dimethyldithiocarbamate (US 1 972 961 ); thiram, bis(dimethylthiocarbamoyl) disulfide (DE 642 532); ziram, dimethyldithiocarbamate; zineb, zinc ethylenebis(dithio- carbamate) (US 2 457 674); diethofencarb, isopropyl 3,4-diethoxycarbanilate; iprovali- carb, isopropyl [(1S)-2-methyl-1-(1-p-tolylethylcarbamoyl)propyl]carbamate (EP-A 472 996); flubenthiavalicarb (benthiavalicarb), isopropyl {(S)-1-[(1 R)-1-(6-fluorobenzothia- zol-2-yl)ethylcarbamoyl]-2-methylpropyl}carbamate (JP-A 09/323 984); propamocarb, propyl 3-(dimethylamino)propylcarbamate (DE 16 43 040); dodine, (2,4-dichlorophen- oxy)acetic acid (US 2 867 562); iminoctadine, bis(8-guanidinooctyl)amine (GB 1 1 14 155); guazatine, mixture of products from the amidation of iminodi(octamethy- lene)diamine, mainly iminoctadine; kasugamycin, 1 L-1 , 3,4/2, 5,6-1 -deoxy-2, 3, 4,5,6- pentahydroxycyclohexyl 2-amino-2,3,4,6-tetradeoxy-4-(α-iminoglycino)-α-D-arabino- hexopyranoside; streptomycin, O-2-deoxy-2-methylamino-α-L-glucopyranosyl-(1 →2)- O-5-deoxy-3-C-formyl-α-L-lyxofuranosyl-(1 →4)N1,N3-diamidino-D-streptamine; polyox- ins, 5-(2-amino-5-O-carbamoyl-2-deoxy-L-xylonamido)-1 -(5-carboxy-1 ,2,3,4-tetrahydro- 2,4-dioxopyrimidin-1-yl)-1 ,5-dideoxy-β-D-allofuranuronic acid and the salts thereof; validamycin A, binapacryl, (RS)-2-sec-butyl-4,6-dinitrophenyl 3-methylcrotonate; dino- cap, the mixture of 2,6-dinitro-4-octylphenyl crotonate and 2,4-dinitro-6-octylphenyl crotonate, wherein "octyl" is a mixture of 1-methylheptyl, 1-ethylhexyl and 1-propyl- pentyl (US 2 526 660); dinobuton, (RS)-2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate; dithianon, 5,10-dioxo-5,10-dihydronaphtho[2,3-b][1 ,4]dithiin-2,3-dicarbonitrile (GB 857 383); isoprothiolane, indol-3-ylacetic acid; fentin acetate, triphenyltin acetate (US 3 499 086); edifenphos, O-ethyl S,S-diphenyl phosphorodithioate; iprobenfos, S- benzyl 0,0-diisopropyl phosphorothioate (Jpn. Pesticide Inf., No. 2, S. 1 1 (1970)); fo- setyl, fosetyl-aluminum, (aluminum) ethylphosphonate (FR 22 54 276); pyrazophos, ethyl 2-diethoxyphosphinothioyloxy-5-methylpyrazolo[1 ,5-a]pyrimidine-6-carboxylate (DE 15 45 790); tolclofos-methyl, 0-2,6-dichloro-p-tolyl 0,0-dimethyl phosphorothioate (GB 14 67 561); chlorothalonil, 2,4,5,6-tetrachloroisophthalonitrile (US 3 290 353); di- chlofluanid, N-dichlorofluoromethylthio-N,N-dimethyl-N-phenylsulfamide (DE 1 1 93 498); flusulfamide, 2',4-dichloro-α,α,α-trifluoro-4'-nitro-m-toluenesulfanilide (EP-A 199 433); hexachlorobenzene (C. R. Seances Acad. Agric. Fr., Vol. 31 , p. 24 (1945)); phthalide (DE 16 43 347); pencycuron, 1-(4-chlorobenzyl)-1-cyclopentyl-3-phenylurea (DE 27 32 257); quintozene, pentachloronitrobenzene (DE 682 048); thiophanate- methyl, 1 ,2-phenylenebis(iminocarbonothioyl)bis(dimethylcarbamate) (DE-OS 19 30 540); tolylfluanid, N-dichlorofluoromethylthio-N,N-dimethyl-N-p-tolylsulfamide (DE 1 1 93 498); Bordeaux mixture, mixture of calcium hydroxide and copper(ll) sulfate; copper hydroxide, Cu(OH)2; copper oxychloride, Cu2CI(OH)3; cyflufenamid, (Z)-N-[α- (cyclopropylmethoxyimino)-2,3-difluoro-6-(trifluoromethyl)benzyl]-2-phenylacetamide (WO 96/19442); cymoxanil, 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea (US 3 957 847); dimethirimol, 5-butyl-2-dimethylamino-6-methylpyrimidin-4-ol (GB 11 82 584); ethirimol, 5-butyl-2-ethylamino-6-methylpyrimidin-4-ol (GB 11 82 584); furalaxyl, methyl N-(2-furoyl)-N-(2,6-xylyl)-DL-alaninate (GB 14 48 810); metrafenone, 3'-bromo-2, 3,4,6'- tetramethoxy-2',6-dimethylbenzophenone (US 5 945 567); spiroxamine, (8-tert-butyl- 1 ,4-dioxaspiro[4.5]dec-2-yl)diethylamine (EP-A 281 842).
The compounds named according to IUPAC, their preparation and their fungicidal activity are likewise known: methyl (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]ben- zyl)carbamate, methyl (2-chloro-5-[1 -(6-methylpyridin-2-ylmethoxyimino)ethyl]ben- zyl)carbamate (EP-A 12 01 648); methyl 2-(ortho-((2,5-dimethylphenyloxymethy- lene)phenyl)-3-methoxyacrylate (EP-A 226 917); 5-chloro-7-(4-methylpiperidin-1-yl)-6- (2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine (WO 98/46608), 3,4-dichloro-N- (2-cyanophenyl)isothiazole-5-carboxamide (WO 99/24413), N-(2-{4-[3-(4-chlorophe- nyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyr- amide, N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethane- sulfonylamino-3-methylbutyramide (WO 04/049804), N-(4'-bromobiphenyl-2-yl)-4-di- fluoromethyl-2-methylthiazole-5-carboxamide, N-(4'-trifluoromethylbiphenyl-2-yl)-4- difluoromethyl-2-methylthiazole-5-carboxamide, N-(4'-chloro-3'-fluorobiphenyl-2-yl)-4- difluoromethyl-2-methylthiazole-5-carboxamide, N-(3',4'-dichloro-4-fluorobiphenyl-2-yl)- 3-difluoromethyl-1-methylpyrazole-4-carboxamide (WO 03/066609); N-(3',4'-dichloro-5- fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide (WO 03/053145); 2-butoxy-6-iodo-3-propylchromen-4-one (WO 03/14103); 3-[5-(4-chloro- phenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine (EP-A 10 35 122); amisulbrom, N, N- dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1 -sulfonyl)-[1 ,2,4]triazole-1 -sulfonamide (WO 03/053145); methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methyl- butyrylamino)propanoate (EP-A 1028125).
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 against pests. One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control.
Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests.
There also exists the need for pest control agents that combine knock-down activity with prolonged control, that is, fast action with long lasting action.
Another difficulty in relation to the use of pesticides is that the repeated and exclusive application of an individual pesticidal compound leads in many cases to a rapid selection of pests, that means animal pests, and harmful fungi, which have developed natu- ral or adapted resistance against the active compound in question. Therefore there is a need for pest control agents that help prevent or overcome resistance.
It was therefore an object of the present invention to provide pesticidal mixtures which solve the problems of reducing the dosage rate and / or enhancing the spectrum of activity and / or combining knock-down activity with prolonged control and / or to resistance management.
We have found that this object is in part or in whole achieved by the combination of active compounds as defined herein. Moreover, we have found that simultaneous (that is, joint or separate) application or sucessive application of a compound I and one or more compounds Il allows enhanced control of pests compared to the control rates that are possible with the individual compounds (synergistic mixtures).
It will be appreciated from the above, that the compounds I and Il can be applied simul- taneously, that is jointly (e.g. in the same formulation) or separately (e.g. in different formulations, such as in kit form), or in succession. If there is a sucessive application, it will also be appreciated that the subsequently applied compounds I and Il should be applied to a subject (e.g. the pest, plant or animal) within a time scale so as to achieve or optimize the above referred to advantageous synergistic effect.
In the definitions of the variables specified in the formulae I, I-A and I-B, collective terms were used which are generally representative of particular substituents. The term Ca-Cb specifies the number of carbon atoms in the particular substituents or substituent moiety which is possible in each case. Other definitions are as follows:
"Halogen" will be taken to mean fluorine, chlorine, bromine, and iodine. The term "halo" refers to fluoro, chloro, bromo, and iodo.
The term "alkyl" as used herein refers to a branched or unbranched saturated hydro- carbon group having 1 to 10 carbon atoms, especially d-Cε-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1 -ethyl-2- methylpropyl.
The term "haloalkyl" as used herein refers to a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C2-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, tri- chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichloro- fluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl.
Similarly, "alkoxy" and "alkylthio" refer to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group. Examples include methoxy, ethoxy, pro- poxy, isopropoxy, methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.
Similarly, "alkylsulfinyl" and "alkylsulfonyl" refer to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above) bonded through - S(=O)- or - S(=O)2- linkages, respectively, at any bond in the alkyl group. Examples include me- thylsulfinyl and methylsulfonyl.
Similarly, "alkylamino" refers to a nitrogen atom which carries 1 or 2 straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above) which may be the same or different. Examples include methylamino, dimethylamino, ethylamino, di- ethylamino, methylethylamino, isopropylamino, or methylisopropylamino.
The term "alkylcarbonyl" refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above) bonded through a -C(=O)- linkage, respectively, at any bond in the alkyl group. Examples include acetyl and propionyl. The term "alkenyl" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 3 to 10 carbon atoms and a double bond in any position, such as C3-C6 alkenyl such as 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl; 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1- butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2- butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3- butenyl, 1 ,1-dimethyl-2-propenyl, 1 ,2-dimethyl-1-propenyl, 1 ,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1- pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2- pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3- pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4- pentenyl, 1 ,1-dimethyl-2-butenyl, 1 ,1-dimethyl-3-butenyl, 1 ,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 -butenyl, 1 ,3-dimethyl-2- butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1 -butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1 -butenyl, 3,3-dimethyl-2- butenyl, 1 -ethyl-1 -butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2- propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.
The term "alkynyl" as used herein refers to a branched or unbranched unsaturated hydrocarbon group containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl and the like.
"Cycloalkyl" refers to a monocyclic 3- to 8-, 10- or 12-membered saturated carbon atom rings, e.g. Cs-Cs-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
The term "aryl" refers to an aromatic carbocyclic group having at least one aromatic ring (e.g., phenyl or biphenyl) or multiple condensed rings in which at least one ring is aromatic (e.g., 1 ,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl), each of which may be substituted.
A 5- to 6-membered aromatic ring containing 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, intends e.g. 5-membered heteroaryl, containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom, e.g. furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadia- zolyl, oxadiazolyl, triazolyl, and tetrazolyl; or 6-membered heteroaryl, containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom, e.g. 2-pyridinyl, 3- pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5- pyrimidinyl, 2-pyrazinyl, 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
A 3- to 6-membered saturated or partially unsaturated ring which contains 1 to 3 het- eroatoms selected from oxygen, sulfur and nitrogen intends e.g. a saturated 3- to 6- membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, such as aziridine, pyrrolidine, tetrahydrofuran, tetrahydropyran, or piperidine.
With a view to the intended use of the amidrazones of the formula I, preference is given to the following meanings of the substituents and indices, in each case on their own or in combination:
In one embodiment of the compounds of formula I, A denotes C-R4.
In a further embodiment of the compounds of formula I, B denotes C-R5.
In a further embodiment of the compounds I, W denotes C-R6.
In a further embodiment of the compounds I, A denotes C-R4, B denotes C-R5, and W denotes C-R6.
In a further embodiment of the compounds I, R4 is halogen or d-Cβ-haloalkyl, preferably halogen, especially chlorine or bromine, with chlorine being most preferred.
In a further embodiment of the compounds I, R5 is hydrogen or halogen, especially hydrogen.
In a further embodiment of the compounds I, R6 is halogen or C-i-Cβ-haloalkyl, preferably Ci-Cβ-haloalkyl, especially trifluoromethyl.
In a further embodiment of the compounds I, Y is halogen or C-i-Cβ-haloalkyl, in particular halogen or C-i-Cβ-haloalkyl which is disposed in the 6-position.
In a further embodiment of the compounds I, Y is halogen, especially chlorine.
In a further embodiment of the compounds I, Y is halogen, in particular chlorine, which is disposed in the 6-position.
In a further embodiment of the compounds I, n is 1. In a further embodiment of the compounds I, R denotes hydrogen or d-Cε-alkyl, in particular hydrogen.
In a further embodiment of the compounds I, R1 and R2 are each independently hydro- gen, Ci-Cio-alkyl which is unsubstituted or substituted by Ci-C4-alkoxy, or
C3-Cio-cycloalkyl which is unsubstituted or substituted with from 1 to 3 halogen.
In a further embodiment of the compounds I, R1 and R2 are each independently hydrogen, Ci-C4-alkyl, or Cs-Cβ-cycloalkyl.
In a further embodiment of the compounds I, R1 is hydrogen and R2 is Ci-Cio-alkyl which is unsubstituted or substituted by Ci-C4-alkoxy, or C3-Cio-cycloalkyl which is unsubstituted or substituted with from 1 to 3 halogen.
In a further embodiment of the compounds I, R1 is hydrogen and R2 is Ci-C4-alkyl or C3-C6-cycloalkyl.
In a further embodiment of the compounds I, R1 is hydrogen and R2 is Ci-C4-alkyl, in particular ethyl.
In a further embodiment of the compounds I, R3 is unsubstituted Ci-Cio-alkyl or C3-Cio-cycloalkyl, which is unsubstituted or substituted with 1 to 5 halogen atoms and/or 1 to 3 d-Cε-alkyl groups.
In a further embodiment of the compounds I, R3 is Ci-Cio-alkyl, in particular C-i-Cε-alkyl, with tert-butyl being the most preferred.
In a further embodiment of the compounds I, R3 is cyclopropyl which is unsubstituted or substituted with d-Cε-alkyl or halogen.
In a further embodiment of the compounds I, R3 is C3-Cio-cycloalkyl which is unsubstituted or substituted with 1 to 5 halogen atoms and/or 1 to 3 d-Cε-alkyl groups and/or 1 to 3 Ci-Cβ-haloalkyl groups.
In a further embodiment of the compounds I, R3 is cyclopropyl which is unsubstituted or substituted with 1 to 3 halogen atoms and/or 1 to 3 d-Cβ-alkyl groups and/or 1 to 3 Ci-Cβ-haloalkyl groups.
In a further embodiment of the compounds I, R3 is cyclopropyl which is substituted with 2 halogen atoms and/or 1 d-Cβ-alkyl group, in particular cyclopropyl which is substituted with 2 chlorine atoms and/or 1 methyl group. In a further embodiment of the compounds I, R3 is a cyclopropyl group of formula III
Figure imgf000017_0001
wherein R7 is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl, and R8, R9, R10 and R11 are each independently selected from hydrogen, halogen, d-Cε-alkyl and d-Cε-haloalkyl.
In a further embodiment of the compounds I, R3 is a cyclopropyl group of formula III wherein R7 is hydrogen, d-Cε-alkyl or C-i-Cε-haloalkyl, R8 and R9 are both halogen, and R10 and R11 are both hydrogen.
In a further embodiment of the compounds I, R3 is a cyclopropyl group of formula III wherein R7 is d-Cε-alkyl, R8 and R9 are both halogen, and R10 and R11 are both hydro- gen.
In a further embodiment of the compounds I, R3 is a cyclopropyl group of formula III wherein R7 is hydrogen, methyl or trifluoromethyl, R8 and R9 are independently selected from fluoro, chloro and bromo, and R10 and R11 are both hydrogen.
In a further embodiment of the compounds I, R3 is a cyclopropyl group of formula III wherein R7 is hydrogen or methyl, R8 and R9 are chloro or bromo, and R10 and R11 are both hydrogen.
In a further embodiment of the compounds I, R3 is a cyclopropyl group of formula III wherein R7 is methyl, R8 and R9 are chloro or bromo, and R10 and R11 are both hydrogen, in particular a cyclopropyl group of formula III wherein R7 is methyl, R8 and R9 are both chloro, and R10 and R11 are both hydrogen, i.e. 1-(2,2-dichloro-1- methylcyclopropyl).
With respect to their use, preference is given to the compounds I-A compiled in the tables below. Moreover, the groups mentioned for a substituent in the tables are on their own, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.
Table 1 Compounds of the formula I-A wherein R3 is methyl and the combination of R1, R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Figure imgf000018_0001
Table 2
Compounds of the formula I-A wherein R3 is ethyl and the combination of R1, R2, R4,
R5, R6 and Yn corresponds in each case to a row of Table A.
Table 3
Compounds of the formula I-A wherein R3 is propyl and the combination of R1, R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table 4 Compounds of the formula I-A wherein R3 is isopropyl and the combination of R1 , R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table 5
Compounds of the formula I-A wherein R3 is isobutyl and the combination of R1, R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table 6
Compounds of the formula I-A wherein R3 is tert-butyl and the combination of R1, R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table 7
Compounds of the formula I-A wherein R3 is neopentyl and the combination of R1, R2,
R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table 8
Compounds of the formula I-A wherein R3 is 1 ,1-dimethyl-propyl and the combination of R1, R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table 9 Compounds of the formula I-A wherein R3 is cyclopropyl and the combination of R1, R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table 10
Compounds of the formula I-A wherein R3 is 1-(2,2-dichloro-cyclopropyl) and the com- bination of R1, R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table 11
Compounds of the formula I-A wherein R3 is 1-(2,2-dibromo-cyclopropyl) and the combination of R1, R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table 12
Compounds of the formula I-A wherein R3 is 1-(1-methyl-cyclopropyl) and the combination of R1, R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table 13
Compounds of the formula I-A wherein R3 is 1-(2,2-dichloro-1-methyl-cyclopropyl) and the combination of R1, R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table 14
Compounds of the formula I-A wherein R3 is 1-(2,2-dibromo-1-methyl-cyclopropyl) and the combination of R1, R2, R4, R5, R6 and Yn corresponds in each case to a row of Table A.
Table A
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0002
With respect to the intended use in the present invention, a specific embodiment relates to the compounds of the formula I-B
Figure imgf000053_0001
wherein
R6 is chlorine or trifluoromethyl;
R4 and Y are each independently chlorine or bromine;
R2 is C-i-Ce-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, or
C3-C6-cycloalkyl which is unsubstituted or substituted with 1 to 3 halogen atoms, or C2-C4-alkyl which is substituted by Ci-C4-alkoxy; and
R3 is Ci-Cβ-alkyl or a cyclopropyl group of formula III as defined herein wherein R7 is hydrogen, d-Ce-alkyl or Ci-C6-haloalkyl, and R8, R9, R10 and R11 are each independently selected from hydrogen, halogen, Ci-Cβ-alkyl and C-i-Cβ-haloalkyl.
In a further embodiment of the compounds of formula I-B, R6 is trifluoromethyl.
In a further embodiment of the compounds I-B, Y and R4 are both chlorine.
In a further embodiment of the compounds I-B, R2 is Ci-Cβ-alkyl, especially ethyl.
In a further embodiment of the compounds I-B, R3 is Ci-Cβ-alkyl, in particular tert-butyl.
In a further embodiment of the compounds I-B, R3 is cyclopropyl which is unsubstituted or substituted by 1 to 3 halogen atoms. In a further embodiment of the compounds I-B, R3 is cyclopropyl which is substituted by 2 halogen atoms, especially chlorine and bromine, and 1 d-Cβ-alkyl group, especially methyl.
In a further embodiment of the compounds I-B, R3 is a cyclopropyl group of formula III wherein R7 is hydrogen, d-Cβ-alkyl or d-Cβ-haloalkyl, R8 and R9 are both halogen, and R10 and R11 are both hydrogen.
In a further embodiment of the compounds I-B, R3 is a cyclopropyl group of formula III wherein R7 is d-Cβ-alkyl, R8 and R9 are both halogen, and R10 and R11 are both hydrogen.
In a further embodiment of the compounds I-B, R3 is a cyclopropyl group of formula III wherein R7 is hydrogen, methyl or trifluoromethyl, R8 and R9 are independently selected from fluoro, chloro and bromo, and R10 and R11 are both hydrogen.
In a further embodiment of the compounds I-B, R3 is a cyclopropyl group of formula III wherein R7 is hydrogen or methyl, R8 and R9 are chloro or bromo, and R10 and R11 are both hydrogen.
In a further embodiment of the compounds I-B, R3 is a cyclopropyl group of formula III wherein R7 is methyl, R8 and R9 are chloro or bromo, and R10 and R11 are both hydrogen.
In a further embodiment of the compounds I-B, R3 is a cyclopropyl group of formula III wherein R7 is methyl, R8 and R9 are both chloro, and R10 and R11 are both hydrogen, i.e. 1 -(2,2-dichloro-1 -methylcyclopropyl).
In a further embodiment of the compounds I-B,
R6 is trifluoromethyl;
Y and R4 are each independently chlorine or bromine;
R2 is d-Cβ-alkyl;
R3 is d-Cβ-alkyl or Cs-Cβ-cycloalkyl which is substituted by 1 or 2 halogen atoms and 1 d-Ce-alkyl.
With respect to the use in the present invention, another specific embodiment relates to the compound of formula 1-1 , i.e. N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro- α ,α ,α -trifluoro-p-tolyl)-hydrazone:
Figure imgf000055_0001
Yet another specific embodiment of the present invention relates to the compound of formula 1-2, i.e. N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6- dichloro-α ,α ,α -trifluoro-p-tolyl)hydrazone:
Figure imgf000055_0002
Agrochemically acceptable salts of the amidrazones of formula I, can also be used in the present invention, such as, for example, conventional salts formed from suitable organic or inorganic acids. Examples of agrochemically acceptable salts of the compounds of formula I include chlorides, bromides, fluorides, hydrogen sulfates, sulfates, dihydrogen phosphates, hydrogen phosphates, phosphates, nitrates, hydrogen carbonates, carbonates, hexafluorosilicates, hexafluorophosphates, benzoates, and the salts of Ci-C4-alkanoic acids, preferably formates, acetates, propionates and butyrates. The scope of the present invention includes isomers of the amidrazones of formula I as defined herein. The term "isomer" is used herein in its broadest sense to include structural isomers (such as, for example, positional isomers and tautomers) and stereoisomers (such as, for example, optical isomers, rotational isomers and E/Z isomers). In cases where the amidrazones of formula I possess asymmetric carbon atoms, the ra- cemates and diastereomers as well as the individual enantiometric forms of the amidrazones I as described herein also form part of the scope of the present invention.
Further preferred embodiments of the mixtures according to the invention relate to combinations of one of the compounds of Tables 1 to 14, in particular one of the pre- ferred compounds I hereinabove, and one of the following active compounds II:
A) azoles, such as cyproconazole, difenoconazole, fluquinconazole, flusilazole, metconazole, propiconazole, prothioconazole, tebuconazole prochloraz, cyazofamid; carbendazim; ethaboxam; B) strobilurins, such as azoxystrobin, enestroburin, fluoxastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin or methyl (2-chloro-5-[1-(3- methylbenzyloxyimino)-ethyl]benzyl)carbamate, methyl (2-chloro-5-[1 -(6- methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate;
C) carboxamides, such as benalaxyl, boscalid, fenhexamid, metalaxyl, ofurace, oxadixyl, dimethomorph; fluopicolide (picobenzamid), zoxamide; mandipropamid;
D) heterocylic compounds, such as fluazinam; cyprodinil, pyrimethanil; dodemorph, iprodione, vinclozolin; famoxadone, fenamidone; amisulbrom;
5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine, captan, folpet;
E) carbamates, such as mancozeb, maneb, metiram, propineb; benthiavalicarb, iprovalicarb, flubenthiavalicarb; methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methyl- butyrylamino)propanoate; and
F) other active compounds, selected from sulfur-containing heterocyclyl compounds: dithianon; organophosphorus compounds: fosetyl, fosetyl-aluminum, phosphorous acid and its salts; organochlorine compounds: chlorothalonil, thiophanate-methyl; inorganic active compounds: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate; others: cymoxanil, metrafenone; growth retardants: prohexadione and its salts.
Preferred embodiments relate to the compositions listed in table B, where in each case one row of table B corresponds to a pesticidal composition comprising the particular compound of the formula I mentioned (component 1 ) and one active compound of the groups mentioned, this active compound preferably being selected from the preferred embodiments defined above. Table B
Figure imgf000057_0001
For use according to the present invention, the mixtures according to the invention, or the compound I and the active compound II, can be converted into customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
The formulations are prepared in a known manner, for example by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants. Solvents/auxiliaries which are suitable are essentially: water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethyl- amides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used, carriers such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethyl- ene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of ligno- sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octyl- phenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol poly- glycol ethers, tributylphenyl polyglycol ethers, tristearylphenyl polyglycol ethers, alkyl- aryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methyl- cellulose.
Suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydro- naphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
Suitable preservatives are for example Dichlorophen und enzylalkoholhemiformal.
Seed Treatment formulations may additionally comprise binders and optionally colorants.
Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are block copolymers EO/PO surfactants but also polyvinyl- alcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyiso- utylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, tylose and copolymers derived from these polymers.
Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are 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 1 12, 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 of a gelling agent is carrageen (Satiagel®).
Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds 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, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.
The following are examples of formulations: 1. Products for dilution with water For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
A Water-soluble concentrates (SL, LS)
10 parts by weight of the active compounds are dissolved with 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound dissolves upon dilution with water. A formulation having an active compound content of 10% by weight is obtained in this manner.
B Dispersible concentrates (DC)
20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion. The active compound content is 20% by weight.
C Emulsifiable concentrates (EC) 15 parts by weight of the active compounds are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The formulation has an active compound content of 15% by weight.
D Emulsions (EW, EO, ES)
25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added into 30 parts by weight of water by means of an emulsifying machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The formulation has an active compound content of 25% by weight.
E Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of the active compounds are comminuted with addition of 10 parts by weight of dispersants and wetters and 70 parts by weight of water or an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound. The active compound content in the formulation is 20% by weight.
F Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of the active compounds are ground finely with addition of 50 parts by weight of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound. The formulation has an active compound content of 50% by weight.
G Water-dispersible powders and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of the active compounds are ground in a rotor- stator mill with addition of 25 parts by weight of dispersants and wetters as well as silica gel. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight.
H Gel formulations (GF)
In a ball mill, 20 parts by weight of the active compounds, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or an organic solvent are ground to give a fine suspension. On dilution with water, a stable suspension having an active compound content of 20% by weight is obtained.
2. Products to be applied undiluted
I Dustable powders (DP, DS)
5 parts by weight of the active compounds are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having an active compound content of 5% by weight.
J Granules (GR, FG, GG, MG)
0.5 part by weight of the active compounds is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active compound content of 0.5% by weight.
K ULV solutions (UL)
10 parts by weight of the active compounds are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted having an active compound content of 10% by weight.
For seed treatment, use is usually made of water-soluble concentrates (LS), suspensions (FS), dustable powders (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF). These formulations can be applied to the seed in undiluted form or, preferably, diluted. Application can be carried out prior to sowing.
In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; the intention is to ensure in each case the finest possible distribution of the active compounds according to the invention. Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %.
The active compounds may also be used successfully in the ultra-low-volume process (ULV), by which it is possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the agents according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
Compositions of this invention may also contain other active ingredients, for example other pesticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These additional ingredients may be used sequentially or in combination with the above- described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
The mixtures of a compound I and a compound Il or the simultaneous, that is joint or separate, use of a compound I and a compound Il are distinguished by being highly active against a wide range of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Peronosporomycetes and Basidiomycetes. Some of them act systemically and can be used in crop protection as foliar fungicides, as fungicides for seed dressing and as soil-acting fungicides.
They are particularly important for controlling a multitude of fungi on various cultivated plants, such as bananas, cotton, vegetable species (for example cucumbers, beans and cucurbits), barley, grass, oats, coffee, potatoes, corn, fruit species, rice, rye, soya, tomatoes, grapevines, wheat, ornamental plants, sugar cane and also on a large num- ber of seeds. They are particularly important in the control of a multitude of fungi on various crop plants, such as bananas, cotton, vegetables (for example cucumbers, beans and cucurbits), barley, grass, oats, coffee, potatoes, corn, fruit, rice, rye, soybeans, tomatoes, grape vines, wheat, ornamental plants, sugar cane and a multiplicity of seeds.
Advantageously, they are suitable for controlling the following plant diseases:
Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis),
Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat,
Aphanomyces spp. on sugar beets and vegetables, Ascochyta species on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley
Bipolaris and Drechslera spp. (Teleomorph: Cochliobolus spp.) on corn (e. g. D. may- dis), cereals (e. g. B. sorokiniana: spot blotch), rice (e. g. B. oryzae) and turfs,
Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley),
Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries
(e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat,
Bremia lactucae (downy mildew) on lettuce, Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms,
Cercospora spp. (Cercospora leaf spots) on corn, rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice,
Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herba- rum (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. (anthracnose) on cotton (e. g. C. gos- sypii), corn (e. g. C. graminicola), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum),
Corticium spp., e. g. C. sasakii (sheath blight) on rice,
Corynespora cassiicola (leaf spots) on soybeans and ornamentals, Cycloconium spp., e. g. C. oleaginum on olive trees, Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals,
Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans, Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans,
Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf,
Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamy- dosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa,
Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose),
Entyloma oryzae (leaf smut) on rice, Epicoccum spp. (black mold) on wheat,
Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum),
Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods, Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum),
Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani on soybeans and F. verticil- lioides on corn, Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn,
Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease),
Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton,
Grainstaining complex on rice,
Guignardia bidwellii (black rot) on vines, Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears,
Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice,
Hemileia spp., e. g. Hemileia 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. para- sitica), 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),
Physorma maydis (brown spots) on corn, Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad-leaved trees (e. g. P. ramorum: sudden oak death)
Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants, Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers,
Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples,
Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and 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. stri- iformis (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 as- paragus (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, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum), 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. so- lani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley,
Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes,
Rhynchosporium secalis (scald) on barley, rye and triticale,
Sarocladium oryzae and S. attenuatum (sheath rot) on rice, Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii),
Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici
(Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals, Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines,
Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf,
Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane,
Sphaerotheca fuliginea (powdery mildew) on cucurbits,
Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases,
Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat,
Synchytrium endobioticum on potatoes (potato wart disease),
Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums,
Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans),
Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat,
Typhula incarnata (grey snow mold) on barley or wheat,
Urocystis 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 und U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane,
Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears, Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
The mixtures of the compounds I and active compounds Il are furthermore suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In the protection of wood, particular attention is paid to the following harmful fungi: Ascomycetes, such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes, such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes, such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes, such as Mucor spp., additionally in the protection of materials the following yeasts: Candida spp. and Saccharomyces cerevisae.
The compounds I and the one or more compound(s) Il are usually applied in a weight ratio of from 500:1 to 1 :100, preferably from 100:1 to 1 :100, more preferably from 20:1 to 1 :20, in particular from 10:1 to 1 :10.
Depending on the type of compound and the desired effect, the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 1500 g/ha, in particular from 50 to 750 g/ha.
When preparing the mixtures, it is preferred to employ the pure active compounds I and II, to which further active compounds against harmful fungi or against other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active compounds or fertilizers can be added as further active components according to need.
Usually, mixtures of a compound I with an active compound Il are employed. However, in certain cases mixtures of the compound I with two or, if appropriate, more active components may be advantageous.
Suitable further active components in the above sense are in particluar the active compounds II, mentioned at the outset and in particular the preferred active compounds mentioned above.
The mixtures of the compounds I and active compounds Il are employed by treating the fungi or the plants, seeds, materials or soil to be protected from fungal attack with a fungicidally effective amount of the active compounds. The application can be carried out both before and after the infection of the materials, plants or seeds by the fungi.
In the method of combating harmful fungi depending on the type of compound and the desired effect, the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 900 g/ha, in particular from 50 to 750 g/ha.
Correspondingly, the application rates for the compound I are generally from 1 to 1000 g/ha, preferably from 10 to 900 g/ha, in particular from 20 to 750 g/ha.
Correspondingly, the application rates for the active compound Il are generally from 1 to 2000 g/ha, preferably from 10 to 900 g/ha, in particular from 40 to 500 g/ha.
The method for controlling harmful fungi is carried out by the separate or joint applica- tion of a compound I and the active compound Il or the mixtures of the compound I and the active compound Il by spraying or dusting the seeds, the plants or the soil before or after sowing of the plants or before or after emergence of the plants.
The treatment can be made into the seedbox before planting into the field.
The compounds I and Il or the mixtures or the corresponding formulations are applied by treating the harmful fungi, the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally effective amount of the mixture or, in the case of separate application, of the compounds I and II. Application can be carried out before or after infection by the harmful fungi.
The mixtures of compounds I and II, or the compounds I and Il used simultaneously, that is jointly or separately, exhibit also outstanding action against pests from the following orders:
insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou- liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo- lesta, Heliothis armigera, Heliothis virescens, Heliothis zea, HeIIuIa undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb- dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocol- letis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseu- dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frus- trana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis,
beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blasto- phagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica Iongicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epila- chna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, lps typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha,
Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sito- philus granaria,
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, An- astrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis,
Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbi- tae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gaster- ophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca domestica, Musca autumnalis, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phor- bia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Sto- moxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa
thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp , Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Re- ticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus,
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
true bugs (Hemiptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis nota- tus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridu- Ia, Piesma quadrata, Solubea insularis , Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gos- sypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachy- caudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Ma- crosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, My- zus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosi- phum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus. ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Lasius niger, Mo- nomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula macula- ta, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile,
crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllo- talpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina,
Arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodo- rus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetra- nychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panony- chus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxos- celes reclusa,
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica,
centipedes (Chilopoda), e.g. Scutigera coleoptrata,
millipedes (Diplopoda), e.g. Narceus spp., Earwigs (Dermaptera), e.g. forficula auricularia,
lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthi- rus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus,
plant parasitic nematodes such as root-knot nematodes, Meloidogyne arenaria, Meloi- dogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica and other Meloidogyne species; cyst nematodes, Globodera rostochiensis, Globodera pallida, Globodera tabacum and other Globodera species, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; seed gall nematodes, Anguina funesta, Anguina tritici and other Anguina species; stem and foliar nematodes, Aphelenchoides besseyi, Aphelen- choides fragariae, Aphelenchoides ritzemabosi and other Aphelenchoides species; sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; ring nematodes, Criconema species, Criconemella species, Criconemoides species, and Me- socriconema species; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus myceliophagus and other Ditylenchus species; awl nematodes, Dolichodorus species; spiral nematodes, Helicotylenchus dihystera, Helicotylenchus multicinctus and other Helicotylenchus species, Rotylenchus robustus and other Roty- lenchus species; sheath nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; lance nematodes, Hoplolaimus columbus, Hoplolai- mus galeatus and other Hoplolaimus species; false root-knot nematodes, Nacobbus aberrans and other Nacobbus species; needle nematodes, Longidorus elongates and other Longidorus species; pin nematodes, Paratylenchus species; lesion nematodes, Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus curvitatus, Pratylenchus goodeyi, Pratylencus neglectus, Pratylenchus penetrans, Pratylenchus scribneri, Praty- lenchus vulnus, Pratylenchus zeae and other Pratylenchus species; Radinaphelen- chus cocophilus and other Radinaphelenchus species; burrowing nematodes, Rado- pholus similis and other Radopholus species; reniform nematodes, Rotylenchulus reni- formis and other Rotylenchulus species; Scutellonema species; stubby root nematodes, Trichodorus primitivus and other Trichodorus species; Paratrichodorus minor and other Paratrichodorus species; stunt nematodes, Tylenchorhynchus claytoni, Tylen- chorhynchus dubius and other Tylenchorhynchus species and Merlinius species; citrus nematodes, Tylenchulus semipenetrans and other Tylenchulus species; dagger nematodes, Xiphinema americanum, Xiphinema index, Xiphinema diversicaudatum and other Xiphinema species; and other plant parasitic nematode species. Moreover, the inventive mixtures are especially useful for the control of Lepidoptera, Coleoptera, Diptera, Thysanoptera and Hymenoptera.
Moreover, the inventive mixtures are especially useful for the control of non-crop pests (household, turf, ornamental).
The mixtures according to the invention can be applied to any and all developmental stages of pests, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the inventive mixtures or of compositions comprising the mixtures.
"Locus" means a plant, seed, soil, area, material or environment in which a pest is growing or may grow.
In general, "pesticidally effective amount" means the amount of the inventive mixtures or of compositions comprising the mixtures needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various mixtures / compositions used in the invention. A pesticidally effective amount of the mixtures / compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
The inventive mixtures or compositions of these mixtures can also be employed for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting a plant, or soil or water in which the plant is growing.
In the context of the present invention, the term plant refers to an entire plant, a part of the plant or the propagation material of the plant, that is, the seed or the seedling.
Plants which can be treated with the inventive mixtures include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures.
Some of the inventive mixtures have systemic action and can therefore be used for the protection of the plant shoot against foliar pests as well as for the treatment of the seed and roots against soil pests. The term seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
The compounds I and the one or more compound(s) Il can be applied simultaneously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
The inventive mixtures are also suitable for the protection of the seed and the seedlings' roots and shoots, preferably the seeds, against soil pests.
Compositions, which are especially useful for seed treatment are e.g.:
A Soluble concentrates (SL, LS) D Emulsions (EW, EO, ES) E Suspensions (SC, OD, FS)
F Water-dispersible granules and water-soluble granules (WG, SG) G Water-dispersible powders and water-soluble powders (WP, SP, WS) H Gel-Formulations (GF) I Dustable powders (DP, DS)
Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. Preferred are FS formulations.
In the treatment of seed, the application rates of the inventive mixture are generally from 0.001 to 10 kg per 100 kg of seed, dependent from the desired effect and the kind of seed. Application rates are preferably from 1 to 1000 g/100 kg of seed, more preferably from 1 to 750 g/100 kg, in particular from 5 to 500 g/100 kg. The separate or joint application of the compounds I and Il or of the mixtures of the compounds I and Il is carried out by spraying or dusting the seeds, the seedlings, the plants or the soils before or after sowing of the plants or before or after emergence of the plants.
The invention also relates to the propagation products of plants, and especially the seed comprising, that is, coated with and/or containing, a mixture as defined above or a composition containing the mixture of two or more active ingredients or a mixture of two or more compositions each providing one of the active ingredients. The seed com- prises the inventive mixtures in an amount of from 0.1 g to 10 kg per 100 kg of seed. The inventive mixtures are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part) and through trophallaxis and transfer.
Preferred application methods are into water bodies, via soil, cracks and crevices, pastures, manure piles, sewers, into water, on floor, wall, or by perimeter spray application and bait.
According to another preferred embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the inventive mixtures are prepared into a bait preparation.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it. This attractant may be chosen from feeding stimulants or para and / or sex phero- mones readily known in the art.
Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with the inventive mixtures and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like, lnsecticidal compositions for application to fibers, fabric, knitgoods, non- wovens, netting material or foils and tarpaulins preferably comprise a composition in- eluding the inventive mixtures, optionally a repellent and at least one binder.
The inventive mixtures and the compositions comprising them can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 2O g per 100 m2.
Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m2 treated material, desirably from 0.1 g to 50 g per m2. lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and / or insecticide.
For use in bait compositions, the typical content of active ingredient is from 0.0001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound. The composition used may also comprise other additives such as a solvent of the active material, a flavoring agent, a preserving agent, a dye or a bitter agent. Its attractiveness may also be enhanced by a special color, shape or texture.
For use in spray compositions, the content of the mixture of the active ingredients is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
For use in treating crop plants, the rate of application of the mixture of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
It was also an object of the present invention to provide mixtures suitable for treating, controlling, preventing and protecting warm-blooded animals, including humans, and fish against infestation and infection by pests. Problems that may be encountered with pest control on or in animals and/or humans are similar to those described at the outset, namely the need for reduced dosage rates, and / or enhanced spectrum of activity and / or combination of knock-down activity with prolonged control and / or resistance management.
This invention also provides a method for treating, controlling, preventing and protecting warm-blooded animals, including humans, and fish against infestation and infection by pests of the orders Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera, and Diptera, which comprises orally, topically or parenterally administering or applying to said animals a pesticidally effective amount of mixtures according to the invention.
The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting a warm-blooded animal or a fish against infestation or infection by pests of the Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera, and Diptera orders which comprises a pesticidally effective amount of a mixture according to the invention. The above method is particularly useful for controlling and preventing infestations and infections in warm-blooded animals such as cattle, sheep, swine, camels, deer, horses, poultry, goats, dogs and cats as well as humans.
Infestations in warm-blooded animals and fish including, but not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas may be controlled, prevented or eliminated by the mixtures according to the invention.
For oral administration to warm-blooded animals, the mixtures according to the invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the mixtures according to the invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the mixture.
Alternatively, the mixtures according to the invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The mixtures according to the invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the mixtures according to the invention may be formulated into an implant for subcutaneous administration. In addition the mixtures according to the invention may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the mixture.
The mixtures according to the invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, spot-on and pour-on for- mulations. For topical application, dips and sprays usually contain 0.5 ppm to 5000 ppm and preferably 1 ppm to 3000 ppm of the inventive compounds. In addition, the mixtures according to the invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
The synergistic action of the mixtures according to the invention was demonstrated by the following microtiter tests.
Use Examples
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The products pyraclostrobin, benthivali- carb, fenhexamid, boscalid and metlaxyl-M were used as commercial finished formulations and diluted with water to the stated concentration of the active compound.
1-2 corresponds to the compound of formula 1-2, i.e. N-Ethyl-2,2-dichloro-1- methylcyclopropane-carboxamide-2-(2,6-dichloro-α ,α ,α -trifluoro-p-tolyl)hydrazone, as described hereinabove.
The stock solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the stated concentrations.
In the case of using Phytophthora infestans, a spore suspension of said fungus in a pea juice-based aqueous nutrient medium was then added. In all other tests, a spore suspension of the stated fungus in a 2 % aqueous biomalt solution was then added.
The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies.
The efficacy (E) was calculated as follows using Abbot's formula:
E = (1 - α/β) - 100 α corresponds to the fungicidal infection of the treated variant in % and β corresponds to the fungicidal infection of the active-free control variant in %
An efficacy of 0 means that the infection level of the treated variant corresponds to that of the active compound-free control plants; an efficacy of 100 means that the treated variants are not infected.
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.
Colby's formula: E = x + y - x - y / 100
E expected efficacy, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b; x efficacy, expressed in % of the untreated control, when using the active compound A at the concentration a; y efficacy, expressed in % of the untreated control, when using the active compound B at the concentration b.
The results of the microtiter tests are shown in Tables I to XXI below:
Table I: Activity against Cochliobolus miyabeanus (Cochmi)
Figure imgf000079_0001
able III: Activity against Fusarium avenaceum (Fusaav)
Figure imgf000080_0001
Table V: Activity against Fusarium poae (Fusapo)
Figure imgf000081_0001
Table Vl: Activity against Gibberella Zeae (Gibbze)
Figure imgf000081_0002
Table VII: Activity against Monographella nivalis (Mongni)
Figure imgf000082_0001
Table IX: Activity against Pseudocercosporella herpotrichoides, R-Type (Psdcha)
Figure imgf000083_0001
Table X: Activity against Pseudocercosporella herpotrichoides, W-Type (Psdche)
Figure imgf000084_0001
Figure imgf000085_0001
Table XIII: Activity against Rhynchosporium secalis (Rhynse)
Figure imgf000086_0001
Table XIV: Activity against Septoria tritici (Septtr)
Figure imgf000087_0001
Table XV: Activity against Colleotrichum truncatum
Figure imgf000088_0001
Table XVII: Activity against Septoria glycines
Figure imgf000089_0001
Table XIX: Activity against Botrytis cinerea (Botrci)
Figure imgf000090_0001
Table XX: Activity against Fusarium culmorum (Fusacu)
Figure imgf000091_0001
Table XXI: Activity against Leptosphaeria nodorum (Leptno)
Figure imgf000092_0001
As can be seen from Tables I to XXI hereinabove, the observed efficacy in all tests performed with mixtures according to the present invention is higher than the efficacy calculated according to Colby's formula. The experimental results clearly demonstrate that the mixtures according to the invention result in a synergism and provide an excellent control of undesired phytopathogenic fungi.

Claims

Claims
1. A pesticidal mixture comprising, as active components:
1 ) an amidrazone of the formula I
Figure imgf000093_0001
wherein
R is hydrogen, d-Cε-alkyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ- alkylaminocarbonyl, or di(Ci-C6-alkyl)-aminocarbonyl,
wherein in each of the above radicals the alkyl group is unsub- stituted or substituted with 1 to 3 substituents independently selected from halogen, cyano, nitro, Ci-Cβ-alkoxy, C2-C6- alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ-haloalkoxy, Ci-C6-alkylthio, Ci-Cβ-haloalkylthio, Ci-Cβ-alkylsulfonyl, Ci-Cβ-alkylsulfinyl, and di(Ci-C6alkyl)-amino;
R1 and R2 are each independently hydrogen, Ci-Cio-alkyl, C3-Cio-alkenyl, C3-Cio-alkynyl, C3-Ci2-cycloalkyl, Ci-Cε-alkylamino, di(Ci-C6-alkyl)- amino, Ci-Cβ-alkylcarbonylamino, Ci-Cβ-alkylsulfonyl, or Ci-Cβ- alkylsulfinyl,
wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups are unsubstituted or substituted with 1 to 3 substituents independently selected from halogen, nitro, cyano, Ci-Cβ-alkoxy, Ci-Cβ-haloalkoxy, C-i-Cε-alkylthio, d-Ce-haloalkylthio, d-Ce-alkylsulfonyl, Ci-C6-alkylsulfinyl,
Ci-Cβ-haloalkylsulfonyl, Ci-Cβ-haloalkylsulfinyl, C3-C6- cycloalkyl, phenyl, and pyridyl;
R3 is Ci-Cio-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, C3-Ci2-cycloalkyl,
wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups are unsubstituted or partially or fully halo- genated and/or substituted with 1 to 3 substituents independently selected from cyano, nitro, hydroxy, mercapto, amino, Ci-Cβ-alkyl, Cs-Cβ-cycloalkyl, C-i-Cβ- alkoxy, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)-amino, d-Cβ-alkylthio, Ci-Cβ-alkylsulfonyl, and Ci-Cβ-alkylsulfinyl, or
a 3- to 6-membered saturated or partially unsaturated ring which may contain 1 to 3 heteroatoms selected from oxygen, sulfur and nitrogen, and which is unsubstituted or substituted with 1 to 5 substituents independently selected from halogen, Ci-Cβ-alkyl, C-i-Cβ-alkylthio, C-i-Cβ-alkylsulfonyl, C-i-Cβ-alkylsulfinyl, Ci-Cβ-alkoxy, d-Cβ-haloalkoxy, nitro and cyano, wherein in each of the above radicals the alkyl group is unsubstituted or substituted with 1 to 3 halogen atoms;
A IS C-R4 or N;
B is C-R5 or N;
W is C-R6 or N;
with the proviso that one of A, B and W is other than N;
R4, R5, R6 are each independently hydrogen, halogen, nitro, cyano, amino, mercapto, hydroxy, Ci-Cio-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, C3-C6-cycloalkyl, Ci-dralkoxy, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)- amino, Ci-dralkylthio, Ci-Cβ-alkylsulfonyl, Ci-Cβ-alkylsulfinyl, or a 5- to 6-membered aromatic ring which may contain 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen;
Y is hydrogen, halogen, cyano, nitro, amino, hydroxy, mercapto, Ci-Cβ-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, Cs-Cβ-cycloalkyl, Ci-dralkoxy, Ci-Cβ-alkylamino, di(Ci-C6)-alkylamino, Ci-dralkylthio, Ci-Cβ-alkylsulfonyl, or Ci-Cβ-alkylsulfinyl; and
n is O, 1 , or 2;
and
2) at least one fungicidal compound Il selected from the following groups:
A) azoles, such as bitertanol, bromuconazole, cyproconazole, difeno- conazole, diniconazole, enilconazole, epoxiconazole, fluquincona- zole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibencona- zole, ipconazole, metconazole, myclobutanil, penconazole, propi- conazole, prothioconazole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole; prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid; benomyl, carbendazim, thiabendazole, fuberidazole; ethaboxam, etridiazole, hymexazole;
B) strobilurins, such as azoxystrobin, dimoxystrobin, enestroburin, fluox- astrobin, kresoxim-methyl, metominostrobin, orysastrobin, picox- ystrobin, pyraclostrobin, trifloxystrobin, or methyl (2-chloro-5-[1-(3- methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1-
(6-methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate, methyl 2- (ortho-((2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate;
C) carboxamides, such as carboxin, benalaxyl, boscalid, fenhexamid, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxa- dixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, N-(4'-bromobiphenyl-
2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4'-trifluoro- methylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carbox- amide, N-(4'-chloro-3'-fluorobiphenyl-2-yl)-4-difluoromethyl-2-me- thylthiazole-5-carboxamide, N-(3',4'-dichloro-4-fluorobiphenyl-2-yl)-3- difluoromethyl-1-methylpyrazole-4-carboxamide, N-(3',4'-dichloro-5- fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carbox- amide; 3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide; dimethomorph, flumorph; flumetover, fluopicolide (picobenzamid), zoxamide; carpropamid, diclocymet, mandipropamid;
N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2- methanesulfonylamino-3-methylbutyramide, N-(2-{4-[3-(4-chloro- phenyl)-prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethanesulfonyl- amino-3-methyl-butyramide;
D) heterocylic compounds, such as fluazinam, pyrifenox; bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil; triforine; fenpiclonil, fludioxonil; aldimorph, dodemorph, fenpropimorph, tridemorph; fenpropidin, iprodione, procymidone, vinclozolin; famoxadone, fenamidone, octhilinone, probenazole; amisulbrom, anilazine, diclomezine, pyroquilon, proquinazid, tricycla- zole; 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyτimidine, 2-butoxy-6-iodo-3-propylchromen-4-one; acibenzolar-S-methyl, captafol, captan, dazomet, folpet, fenoxanil, quinoxyfen; 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyri- dine;
E) carbamates, such as mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram; benthiavalicarb, diethofencarb, iprovalicarb, flubenthiavalicarb, propamocarb; methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methyl- butyrylamino)propanoate; and F) other active compounds, selected from guanidines: dodine, iminoctadine, guazatine; antibiotics: kasugamycin, streptomycin, polyoxine, validamycin A; nitrophenyl derivates: binapacryl, dinocap, dinobuton; sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane; organometal compounds: fentin salts, such as fentin-acetate; organophosphorus compounds: edifenphos, iprobenfos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, tolclo- fos-methyl; organochlorine compounds: chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate- methyl, tolylfluanid; inorganic active compounds: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; others: cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone and spiroxamine;
in a synergistically effective amount.
2. The pesticidal mixture according to claim 1 , comprising a compound of the for- mula I and a compound Il in a weight ratio of from 100:1 to 1 :100.
3. The pesticidal mixture according to claim 1 or 2, comprising as component 1 a compound of formula I wherein A denotes C-R4 wherein R4 is halogen or Ci-Cβ- haloalkyl, B denotes C-R5 wherein R5 is hydrogen or halogen, W denotes C-R6 wherein R6 is halogen or d-Cβ-haloalkyl, Y is a halogen atom in the 6 position of the aromatic ring, n is 1 , R is hydrogen or Ci-Cβ-alkyl, R1 is hydrogen, R2 is C1-C4- alkyl, R3 is Ci-Cio-alkyl or a cyclopropyl group of the formula III
Figure imgf000097_0001
wherein R7 is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl, and R8, R9, R10 and R11 are each independently selected from hydrogen, halogen, Ci-Cβ-alkyl or C-i-Ce-haloalkyl.
4. The pesticidal mixture according to any of claims 1 to 3, comprising as compo- nent 1 a compound of formula I wherein A is C-Cl, B is CH, W is C-CF3, Y is a chlorine atom in the 6 position of the aromatic ring, n is 1 , R and R1 are both hydrogen, R2 is ethyl and R3 is tert-butyl or 1-(2,2-dichloro-1-methyl- cyclopropyl).
5. A ternary pesticidal mixture according to any of claims 1 to 4, comprising two active compounds II.
6. A pesticidal composition, comprising a liquid or solid carrier and a mixture as claimed in any of claims 1 to 5.
7. A process for preparing the composition according to claim 6, said process comprising the step of extending the compounds I and Il as defined in any of claims
1 , 3 or 4 with a liquid or solid carrier.
8. A method for controlling phytopathogenic harmful fungi, wherein the fungi, their habitat or the plants to be protected against fungal attack, or the soil are treated with an effective amount of the compounds I and Il as defined in any of claims 1 , 3 or 4 or of the mixture as claimed in any of claims 1 to 5.
9. A method for controlling insects, arachnids or nematodes comprising contacting the insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with the compounds I and Il as defined in any of claims 1 , 3 or 4 or of the mixture as claimed in any of claims 1 to 5 in pesticidally effective amounts.
10. A method for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or the soil or water in which the plant is growing, with the compounds I and Il as defined in any of claims 1 , 3 or 4 or of the mixture as claimed in any of claims 1 to 5 in pesticidally effective amounts.
1 1. A method according to any of claims 8 to 10, wherein the compounds I and Il as defined in any of claims 1 , 3 or 4 are applied or the mixture as claimed in any of claims 1 to 5 is applied in an amount of from 5 g/ha to 2000 g/ha.
12. A method for protection of seed comprising contacting the seeds with the compounds I and Il as defined in any of claims 1 , 3 or 4 or the mixture as claimed in any of claims 1 to 5 in pesticidally effective amounts.
13. The method according to claim 12 wherein the compounds I and Il as defined in any of claims 1 , 3 or 4 or the mixture as claimed in any of claims 1 to 5 is applied in an amount of from 0.001 g to 10 kg per 100 kg of seeds.
14. The method according to any of claims 8 to 14 wherein the compounds I and Il as defined in any of claims 1 , 3 or 4 are applied simultaneously, that is jointly or separately, or in succession.
15. Seed, comprising the mixture as claimed in any of claims 1 to 5 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.
PCT/EP2008/050927 2007-02-01 2008-01-28 Pesticidal mixtures WO2008092818A2 (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010043552A1 (en) * 2008-10-16 2010-04-22 Basf Se Pesticidal mixtures comprising metaflumizone and an azole fungicide
WO2010043553A1 (en) * 2008-10-16 2010-04-22 Basf Se Pesticidal mixtures comprising metaflumizone and a fungicidal compound
CN102007918A (en) * 2010-11-25 2011-04-13 陕西美邦农药有限公司 Bactericidal composition containing cyproconazole and jinggangmycin
CN102113485B (en) * 2009-12-30 2013-03-13 青岛奥迪斯生物科技有限公司 Bactericidal composition containing ethirimol and kresoxim-methyl
CN104621149A (en) * 2013-11-15 2015-05-20 南京华洲药业有限公司 Sterilization composition containing prothioconazole and thifluzamide and application thereof
CN106070223A (en) * 2012-03-26 2016-11-09 陕西韦尔奇作物保护有限公司 A kind of bactericidal composition containing mepanipyrim and methoxy acrylic

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB736473A (en) * 1952-09-25 1955-09-07 Bataafsche Petroleum Compositions for combating parasites
US3786094A (en) * 1970-09-17 1974-01-15 Roussel Uclaf Novel phenylhydrazones
EP0604798A1 (en) * 1992-12-29 1994-07-06 American Cyanamid Company N-arylhydrazine derivatives as insecticidal and acaricidal agents
WO2005053401A2 (en) * 2003-12-04 2005-06-16 Basf Aktiengesellschaft N-arylhydrazine derivatives for seed treatment
WO2006128863A1 (en) * 2005-06-03 2006-12-07 Basf Aktiengesellschaft Pesticidal mixture
WO2006128865A1 (en) * 2005-06-03 2006-12-07 Basf Aktiengesellschaft Method of combating bugs

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB736473A (en) * 1952-09-25 1955-09-07 Bataafsche Petroleum Compositions for combating parasites
US3786094A (en) * 1970-09-17 1974-01-15 Roussel Uclaf Novel phenylhydrazones
EP0604798A1 (en) * 1992-12-29 1994-07-06 American Cyanamid Company N-arylhydrazine derivatives as insecticidal and acaricidal agents
WO2005053401A2 (en) * 2003-12-04 2005-06-16 Basf Aktiengesellschaft N-arylhydrazine derivatives for seed treatment
WO2006128863A1 (en) * 2005-06-03 2006-12-07 Basf Aktiengesellschaft Pesticidal mixture
WO2006128865A1 (en) * 2005-06-03 2006-12-07 Basf Aktiengesellschaft Method of combating bugs

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010043552A1 (en) * 2008-10-16 2010-04-22 Basf Se Pesticidal mixtures comprising metaflumizone and an azole fungicide
WO2010043553A1 (en) * 2008-10-16 2010-04-22 Basf Se Pesticidal mixtures comprising metaflumizone and a fungicidal compound
CN102113485B (en) * 2009-12-30 2013-03-13 青岛奥迪斯生物科技有限公司 Bactericidal composition containing ethirimol and kresoxim-methyl
CN102007918A (en) * 2010-11-25 2011-04-13 陕西美邦农药有限公司 Bactericidal composition containing cyproconazole and jinggangmycin
CN106070223A (en) * 2012-03-26 2016-11-09 陕西韦尔奇作物保护有限公司 A kind of bactericidal composition containing mepanipyrim and methoxy acrylic
CN106070223B (en) * 2012-03-26 2018-11-20 陕西韦尔奇作物保护有限公司 A kind of bactericidal composition containing mepanipyrim and methoxy acrylic
CN104621149A (en) * 2013-11-15 2015-05-20 南京华洲药业有限公司 Sterilization composition containing prothioconazole and thifluzamide and application thereof

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