US20180360041A1 - Use of Strobilurin Type Compounds for Combating Phytopathogenic Fungi Resistant to QO Inhibitors - Google Patents

Use of Strobilurin Type Compounds for Combating Phytopathogenic Fungi Resistant to QO Inhibitors Download PDF

Info

Publication number
US20180360041A1
US20180360041A1 US16/112,176 US201816112176A US2018360041A1 US 20180360041 A1 US20180360041 A1 US 20180360041A1 US 201816112176 A US201816112176 A US 201816112176A US 2018360041 A1 US2018360041 A1 US 2018360041A1
Authority
US
United States
Prior art keywords
methyl
alkyl
phenyl
inhibitors
individualized compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US16/112,176
Inventor
Joachim Rheinheimer
Violeta Terteryan
Stefan Redlich
Doris Kremzow
Claudia Rosenbaum
Sebastian Georgios Rohrer
Wassilios Grammenos
Christian Pilger
Franz Roehl
Markus Gewehr
Gerd Stammler
Jurith Montag
Hubert Sauter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=47290995&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20180360041(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by BASF SE filed Critical BASF SE
Priority to US16/112,176 priority Critical patent/US20180360041A1/en
Publication of US20180360041A1 publication Critical patent/US20180360041A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms

Definitions

  • the present invention relates to the use of strobilurine type compounds of formula I and the N-oxides and the salts thereof for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, and to methods for combating such fungi.
  • the invention also relates to novel compounds, processes for preparing these compounds, to compositions comprising at least one such compound, to plant health applications, and to seeds coated with at least one such compound.
  • Qo inhibitor fungicides often referred to as strobilurin-type fungicides (Sauter 2007: Chapter 13.2. Strobilurins and other complex III inhibitors. In: Krämer, W.; Schirmer, U. (Ed.)—Modern Crop Protection Compounds. Volume 2. Wiley-VCH Verlag 457-495), are conventionally used to control a number of fungal pathogens in crops.
  • Qo inhibitors typically work by inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bc 1 complex (electron transport complex III) in mitochondria. Said oxidation center is located on the outer side of the inner mitochrondrial membrane.
  • a prime example of the use of Qo inhibitors includes the use of, for example, strobilurins on wheat for the control of Septoria tritici (also known as Mycosphaerella graminicola ), which is the cause of wheat leaf blotch.
  • Septoria tritici also known as Mycosphaerella graminicola
  • Unfortunately, widespread use of such Qo inhibitors has resulted in the selection of mutant pathogens which are resistant to such Qo inhibitors (Gisi et al., Pest Manag Sci 56, 833-841, (2000). Resistance to Qo inhibitors has been detected in several phytopathogenic fungi such as Blumeria graminis, Mycosphaerella fijiensis, Pseudoperonspora cubensis or Venturia inaequalis .
  • new methods and compositions are desirable for controlling pathogen induced diseases in crops comprising plants subjected to pathogens that are resistant to Qo inhibitors.
  • the fungicidal activity of the known fungicidal strobilurin analogue compounds is unsatisfactory, especially in case that a high proportion of the fungal pathogens contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors. Based on this, it was also an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic harmful fungi.
  • Qo inhibitor includes any substance that is capable of diminishing and/or inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bc 1 complex in mitochondria.
  • the oxidation center is typically located on the outer side of the inner mitochrondrial membrane.
  • Qi inhibitors typically work by inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bcl complex in mitochondria, the said oxidation center being located on the inner side of the inner mitochrondrial membrane.
  • the strobilurin-analogue compounds according to the present invention differ from those described in the abovemention publication by the specific formula I and by inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bcl complex in mitochondria which defines them as Qo inhibitors.
  • these compounds contain two specific carbon atoms bound by a double bond wherein the groups R 1 and R 2 are cis-oriented or the R 1 and R 2 together with the abovementioned two carbon atoms linking them form a phenyl ring if R 4 is 4-methyl-1,4-dihydro-tetrazol-5-on-1-yl.
  • the present invention also relates to methods for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors using the abovementioned compounds of formula I.
  • strobilurin type compounds wherein R 1 and R 2 together with the two carbon atoms linking them form a phenyl ring and wherein R 4 is 1-methyl-1,4-dihydro-tetrazole-5-one-4-yl (R4-7) are known inter alia from WO 1996/036229, WO 1999/046246 and DE 199 00 571 A1.
  • the compounds according to the present invention differ from those described in the abovementioned publications that R 1 and R 2 do not form with the two carbon atoms linking them a phenyl ring, and that (E)-2-[1-methoxy-meth-(E)-ylidene]-5-(4-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester (207852-99-1); (E)-2-[1-methoxy-meth-(E)-ylidene]-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester (207853-00-7); (E)-2-[1-methoxy-meth-(E)-ylidene]-4-methyl-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester; (E)-5,5,5-trifluoro-2-[1-methoxy-meth
  • FIG. 1 The commercially available strobilurin analogue compound Pyraclostrobin modelled into an artificial cytochrome bc 1 complex Qo-binding site displays steric clash of the phenyl ring with the 143A methyl group as indicated by arrow in the upper right part of the picture (see left picture). Compound I-6 according to the present invention does not show a steric clash (see right picture).
  • the compounds I can be obtained by various routes in analogy to prior art processes known (e.g. WO 1998/021174, J Organomet Chem 689, 575-584 (2004), WO 1996/036229) and, advantageously, by the synthesis shown in the following schemes and in the experimental part of this application.
  • a suitable method to prepare compounds I is illustrated in scheme 1. It starts with the reduction of an acetylene compound II with a reducing agent like lithium aluminium hydride preferably in the presence of a solvent.
  • Suitable solvents are inert against the reducing agent used and preferably selected from cyclic or aliphatic ethers like diethyl ether, tetrahydrofurane (THF), 1,4-dioxane, and methyl-tert.-butyl ether (MTBE).
  • the reaction temperature can be between ⁇ 40° C. and 100° C., preferably ⁇ 20 to 60° C.
  • a tin compound of formula III wherein Alk defines a suitable alkyl residue like methyl, ethyl, n-propyl, or n-butyl and wherein L is a leaving group such as halogen, ethoxy and methoxy, in particular methoxy, is added.
  • the resulting intermediate IV is a stable compound which can be isolated and purified with the usual methods (for example extraction and chromatography).
  • Compound VI is then coupled with compound VII, wherein LG is a leaving group, preferably being halogen (except fluoro) or a sulfonyloxy group such as triflate, preferably in the presence of a suitable catalyst such as known transition metal catalysts, more preferably palladium catalysts, wherein the ligand may be trifurylphoshine, triphenyl phosphine, tritolyl phosphine or bidentate phosphine ligands.
  • a suitable catalyst such as known transition metal catalysts, more preferably palladium catalysts, wherein the ligand may be trifurylphoshine, triphenyl phosphine, tritolyl phosphine or bidentate phosphine ligands.
  • Copper compounds, such as CuI 2 can be added to improve the reaction.
  • solvents is possible here, with THF, 1,4-dioxane and amides like dimethylformamide (DMF) being preferred.
  • the compound X can be obtained for example from compound VI by direct reaction with iodine.
  • the iodine in compounds X may be replaced by other suitable leaving groups, for example by bromine, chlorine or triflate.
  • the sodium atom in the salt VII can be replaced by other suitable metal atoms, for example potassium, lithium, magnesium, calcium, etc.
  • the coupling reaction of X and XI is performed preferably in the presence of a transition metal catalyst being preferably copper in the presence of a nitrogen containing ligand system (see e.g.: Tetrahedron Lett 2008, 49 (26), 4196-4199; Org Lett. 2004, 6 (11), 1809-1812).
  • C n -C m indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • C 1 -C 6 -alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl (isobutyl), 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methyl pentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl,
  • C 1 -C 4 -haloalkyl refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms (as defined above), wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloro
  • C 1 -C 6 -alkoxy refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkyl group, e.g. OCH 3 , OCH 2 CH 3 , O(CH 2 ) 2 CH 3 , 1-methylethoxy, O(CH 2 ) 3 CH 3 , 1-methyl ⁇ propoxy, 2-methylpropoxy or 1,1-dimethylethoxy, O(CH 2 ) 4 CH 3 or O(CH 2 ) 5 CH 3 .
  • C 1 -C 4 -alkoxy refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms which is bonded via an oxygen, at any position in the alkyl group.
  • C 1 -C 4 -haloalkoxy refers to a C 1 -C 4 -alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, for example, OCH 2 F, OCHF 2 , OCF 3 , OCH 2 Cl, OCHCl 2 , OCCl 3 , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloro ⁇ ethoxy, 0C 2 F 5 , 2-fluoropropoxy, 3-flu
  • C 1 -C 6 -haloalkoxy refers to a C 1 -C 6 -alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above.
  • C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl refers to alkyl having 1 to 4 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a C 1 -C 4 -alkoxy group.
  • C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl refers to alkyl having 1 to 6 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a C 1 -C 6 -alkoxy group.
  • C 1 -C 4 -alkylamino refers to an amino radical carrying one C 1 -C 4 -alkyl group as substituent, e.g. methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1,1-dimethylethylamino and the like.
  • C 1 -C 6 -alkylamino refers to an amino radical carrying one C 1 -C 6 -alkyl group as substituent.
  • di(C 1 -C 4 -alkyl)amino refers to an amino radical carrying two identical or different C 1 -C 4 -alkyl groups as substituents, e. g. dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-N methylamino, N-(n-butyl)-N-methylamino, N-(2-butyl)-N methylamino, N-(isobutyl)-N-methylamino, and the like.
  • di(C 1 -C 6 -alkyl)amino refers to an amino radical carrying two identical or different C 1 -C 6 -alkyl groups as substituents.
  • C 1 -C 4 -alkoxyimino refers to a divalent imino radical (C 1 -C 4 -alkyl-O—N ⁇ ) carrying one C 1 -C 4 -alkoxy group as substituent, e.g. methylimino, ethylimino, propylimino, 1-methylethylimino, butylimino, 1-methylpropylimino, 2-methylpropylimino, 1,1-dimethylethylimino and the like.
  • C 1 -C 6 -alkoxyimino-C 1 -C 4 -alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein two hydrogen atoms of one carbon atom of the alkyl radical are replaced by a divalent C 1 -C 6 -alkoxyimino radical (C 1 -C 6 -alkyl-O—N ⁇ ) as defined above.
  • C 2 -C 6 -alkenyloxyimino-C 1 -C 4 -alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein two hydrogen atoms of one carbon atom of the alkyl radical are replaced by a divalent C 2 -C 6 -alkenyloxyimino radical (C 2 -C 6 -alkenyl-O—N ⁇ ).
  • C 2 -C 6 -alkynyloxyimino-C 1 -C 4 -alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein two hydrogen atoms of one carbon atom of the alkyl radical are replaced by a divalent C 2 -C 6 -alkynyloxyimino radical (C 2 -C 6 -alkynyl-O—N ⁇ ).
  • C 1 -C 4 -alkylcarbonyl refers to a C 1 -C 4 -alkyl radical which is attached via a carbonyl group.
  • (C 1 -C 6 -alkoxy)carbonyl refers to a C 1 -C 6 -alkoxy radical which is attached via a carbonyl group.
  • C 1 -C 6 -alkylaminocarbonyl refers to a C 1 -C 6 -alkylamino radical which is attached via a carbonyl group.
  • di(C 1 -C 6 -alkyl)aminocarbonyl refers to a di(C 1 -C 6 )alkylamino radical which is attached via a carbonyl group.
  • C 2 -C 4 -alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and a double bond in any position, e.g. ethenyl, 1-propenyl, 2-propenyl (allyl), 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl.
  • C 2 -C 6 -alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position.
  • C 2 -C 4 -alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and containing at least one triple bond, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl.
  • C 2 -C 6 -alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and at least one triple bond.
  • C 3 -C 6 -cycloalkyl refers to monocyclic, bicyclic, saturated hydrocarbon radicals having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • C 3 -C 6 -cycloalkenyl refers to unsaturated hydrocarbon radicals having 3 to 6 carbon ring members and a double bond in any position, such as cyclopropenyl, cyclobutenyl, cyclopentenyl or cyclohexenyl.
  • C 3 -C 6 -cycloalkyl-C 1 -C 4 -alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical having 3 to 6 carbon atoms.
  • phenyl-C 1 -C 4 -alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a phenyl radical.
  • Agriculturally acceptable salts of compounds I encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I.
  • Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four C 1 -C 4 -alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C 1 -C 4 -alkyl)sulfonium, and s
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the compounds of formula I can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
  • the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or diastereomers and their mixtures are subject matter of the present invention.
  • the embodiments of the intermediates correspond to the embodiments of the compounds I.
  • the invention also relates to a method for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, comprising: treating the phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors with an effective amount of at least one compound I, or a composition comprising it thereof.
  • the term “phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors” is to be understood that at least 10% of the fungal isolates to be controlled contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, more preferably at least 30%, even more preferably at least 50%, and most preferably at least 75% of the fungi, in particular between 90 and 100%.
  • the method for combating phytopathogenic fungi comprises: a) identifying the phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi as defined herein, and b) treating said fungi or the materials, plants, the soil or seeds with an effective amount of at least one compound I, or a composition comprising it thereof.
  • the invention also relates to a method for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, comprising: treating the phytopathogenic fungi whereof at least 10% contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors with an effective amount of at least one compound I, or a composition comprising it thereof; more preferably at least 30%, even more preferably at least 50%, and most preferably at least 75% of the fungi contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors.
  • the mutation in the mitochondrial cytochrome b gene of the phytopathogenic fungi is G143A.
  • the phytopathogenic fungi are selected from the group consisting of basidomycetes, ascomycetes, and oomycetes.
  • the phytopathogenic fungi are selected from the group consisting of Alternaria alternata, Blumeria graminis, Pyricularia oryzae (also known as Magnaporthe grisea ), Septoria tritici (also known as Mycosphaerella graminicola ), Mycosphaerella fijiensis, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici - repentis and Plasmopara viticola , in particular Septoria tritici.
  • R 1 is halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -alkenyloxy, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl or C 3 -C 6 -cycloalkyl-C 1 -C 4 -alkyl, wherein the aliphatic moieties of R 1 may carry 1, 2, 3 or up to the maximum number of identical or different groups R b which independently of one another are selected from halogen, CN, nitro, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl and C 1 -C 4 -haloalkoxy; more preferably R 1 is halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4
  • R 4 is 1-methoxycarbonyl-2-methoxy-ethen-1-yl (R4-2, wherein X is O), R 1 cannot be CF 3 .
  • R 2 is hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl or C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl; more preferably R 2 is hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, or C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl; even more preferably R 2 is hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy; in particular hydrogen.
  • R 2 is halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -alkenyloxy, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl or C 3 -C 6 -cycloalkyl-C 1 -C 4 -alkyl, wherein the aliphatic moieties of R 2 may carry 1, 2, 3 or up to the maximum number of identical or different groups R a which independently of one another are selected from halogen, CN, nitro, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl and C 1 -C 4 -haloalkoxy.
  • Z is hydrogen or methyl, in particular methyl.
  • Y is a divalent group selected from —OCH 2 —, —CH 2 —, —CH 2 CH 2 —, —C(CH 3 ) ⁇ N—O—CH 2 —, —O—N ⁇ C(CH 3 )—C(CH 3 ) ⁇ N—O—CH 2 — and —C( ⁇ N—O—CH 3 )—C(CH 3 ) ⁇ NO—CH 2 —; preferably —OCH 2 —, —CH 2 CH 2 —, —C(CH 3 ) ⁇ N—O—CH 2 —, —O—N ⁇ C(CH 3 )—C(CH 3 ) ⁇ N—O—CH 2 — or —C( ⁇ N—O—CH 3 )—C(CH 3 ) ⁇ N—O—CH 2 —, where the bond depicted on the left side of the divalent group Y is attached to R 3 , and the bond depicted on the right side is attached to the carbon atom being substitute
  • Y is —CH 2 —, which compounds are of formula I.2:
  • Y is —CH 2 CH 2 —, which compounds are of formula I.3:
  • Y is —C(CH 3 ) ⁇ N—O—CH 2 —, which compounds are of formula I.4:
  • Y is —O—N ⁇ C(CH 3 )—C(CH 3 ) ⁇ N—O—CH 2 —, which compounds are of formula I.5:
  • Y is —C( ⁇ N—O—CH 3 )—C(CH 3 ) ⁇ N—O—CH 2 —, which compounds are of formula I.6:
  • Particularly preferred embodiments of the invention relate to compounds I, wherein the group Y is one of the following radicals Y-1 to Y-10, where the bond depicted on the left side of the divalent group Y is attached to R 3 , and the bond depicted on the right side is attached to the carbon atom being substituted by R 2 :
  • Particularly preferred embodiments of the invention relate to compounds I, wherein the group Y is —OCH 2 —.
  • R 3 is phenyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl wherein the ring member atoms of the heterocyclyl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, wherein R 3 may carry 1, 2, 3, 4 or up to the maximum possible number of identical or different groups R b as defined herein; more preferably said 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl is a 5- to 6-membered heteroaryl wherein the ring member atoms of the heteroaryl include besides carbon atoms 1, 2 or 3 heteroatoms selected from the group of N, O and S.
  • R 3 is phenyl, wherein the phenyl may carry 1, 2, 3, 4 or up to the maximum possible number of identical or different groups R b as defined herein.
  • R 3 is a 5-membered-heteroaryl, wherein the ring member atoms of the heterocyclyl include besides carbon atoms 1, 2 or 3 heteroatoms selected from the group of N, O and S, wherein the heteroaryl may carry 1, 2, 3, 4 or up to the maximum possible number of identical or different groups R b as defined herein; more preferably said heteroaryl is pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl or 1,2,4-thiadiazolyl.
  • R 3 is pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl or 1,2,4-thiadiazolyl, which is substituted by phenyl, wherein said phenyl may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R c , which may be the same or different to any other R c , wherein R c is halogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkoxyimino-C 1 -C 4 -alkyl, phenyl or a 5-membered saturated, partially unsatur
  • R 3 is a 6-membered-heteroaryl, wherein the ring member atoms of the heterocyclyl include besides carbon atoms 1, 2 or 3 heteroatoms selected from the group of N, O and S, wherein the heteroaryl may carry 1, 2, 3, 4 or up to the maximum possible number of identical or different groups R b as defined herein; more preferably said heteroaryl is pyridinyl or pyrimidinyl.
  • R 3 carries 1, 2 or 3 identical or different groups R b .
  • R b independently of one another are selected from carboxyl, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylamino, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylcarbonyloxy, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; and wherein the aforementioned phenyl and heterocyclyl groups R b are attached via a direct bond, an oxygen or sulfur atom.
  • the aliphatic or cyclic groups R b for their part carry 1, 2, 3 or up to the maximum possible number of identical or different groups R c , which, may be the same or different to any other R c , selected from halogen, hydroxyl, nitro, CN, carboxyl, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 8 -alkynyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy; more preferably R b for their part carry 1, 2 or 3 identical or different groups R c .
  • R c which, may be the same or different to any other R c , is halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxyimino-C 1 -C 4 -alkyl, phenyl or a 5-membered saturated, partially unsaturated or aromatic heterocyclyl which, in addition to carbon atoms, contains one to three heteroatoms from the group consisting of N, O and S as ring members; wherein the aforementioned cyclic groups R c are attached via a direct bond, an oxygen or sulfur atom and for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R d as defined herein.
  • two radicals R b that are bound to adjacent ring member atoms of the cyclic group R 3 form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic cycle, which may be a carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S.
  • R 3 is —CR A ⁇ N—O—R B , wherein R A is amino, hydroxyl, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, C 1 -C 4 -alkoxyimino-C 1 -C 4 -alkyl, C 1 -C 4 -alkylamino, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylcarbonyloxy, phenyl, naphthyl or
  • R 3 is —CR A ⁇ N—O—R B , wherein R B is hydroxyl, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, C 1 -C 4 -alkoxyimino-C 1 -C 4 -alkylC 1 -C 4 -alkoxycarbonyl, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members, where the aliphatic or cyclic groups R B may carry 1, 2, 3 or up to the maximum possible number of identical or different
  • R A and R B independently of each other, are C 1 -C 4 -alkyl which may carry 1, 2, 3 or up to the maximum possible number of identical or different halogen; in particular R A and R B are methyl.
  • the aliphatic or cyclic groups R A and/or R B for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups R e , more preferably they carry 0, 1 or 3 identical or different groups R e .
  • R e which may be the same or different to any other R e , is halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy.
  • R 4 is —C( ⁇ NOCH 3 )—CONHCH 3 , —C( ⁇ NOCH 3 )—COOCH 3 , —C( ⁇ CHOCH 3 )—COOCH 3 , —C( ⁇ CHOCH 3 )—CONHCH 3 , —N(OCH 3 )—COOCH 3 , —N(CH 3 )—COOCH 3 or —N(CH 2 CH 3 )—COOCH 3
  • R 4 is R4-1 as defined herein, wherein X is O.
  • R 4 is R4-1 as defined herein, wherein X is NH.
  • R 4 is R4-2 as defined herein, wherein X is O.
  • R 4 is R4-2 as defined herein, wherein X is NH.
  • R 4 is R4-3 as defined herein, wherein X is O.
  • R 4 is R4-3 as defined herein, wherein X is NH.
  • R 4 is R4-4 as defined herein, wherein X is O.
  • R 4 is R4-4 as defined herein, wherein X is NH.
  • R 5 is C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy, more preferably C 1 -C 2 -alkyl or C 1 -C 2 -alkoxy, even more preferably methyl, ethyl or methoxy.
  • R 4 is R4-4 as defined herein, wherein X is O and wherein R 5 is methyl, ethyl or methoxy.
  • R 4 is R4-5 as defined herein, wherein X is O.
  • R 4 is R4-5 as defined herein, wherein X is NH.
  • R 4 is R4-6 as defined herein.
  • R 4 is R4-7 as defined herein.
  • Particularly preferred embodiments of the invention relate to compounds I, wherein the group R 3 is one of the following radicals R3-1 to R3-195, wherein # indicates the point of attachment to the linker moiety Y:
  • R3-1 R3-2 R3-3 R3-4 R3-5 R3-6 R3-7 R3-8 R3-9 R3-10 R3-11 R3-12 R3-13 R3-14 R3-15 R3-16 R3-17 R3-18 R3-19 R3-20 R3-21 R3-22 R3-23 R3-24 R3-25 R3-26 R3-27 R3-28 R3-29 R3-30 R3-31 R3-32 R3-33 R3-34 R3-35 R3-36 R3-37 R3-38 R3-39 R3-40 R3-41 R3-42 R3-43 R3-44 R3-45 R3-46 R3-47 R3-48 R3-49 R3-50 R3-51 R3-52 R3-53 R3-54 R3-55 R3-56 R3-57 R3-58 R3-59 R3-60 R3-61 R3-62 R3-63 R3-64 R3-65 R3-66 R3-67 R3-68 R3-69 R3-70 R3-71 R3-72 R3-73 R3-74 R3-75 R3-
  • Preferred embodiments of the invention relate to compounds I, wherein the group R 3 is R3-A, in particular R3-1 (1-(4-chlorophenyl)-pyrazol-3-yl).
  • the compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • compounds I and compositions thereof are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • field crops such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • treatment of plant propagation materials with compounds I and compositions thereof, respectively is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • cultiva plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. cf. http://cera-gmc.org/, see GM crop database therein).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted posttranslational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • the compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
  • Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. candida ) and sunflowers (e. g. A. tragopogonis ); Alternaria spp. ( Alternaria leaf spot) on vegetables, rape ( A. brassicola or brassicae ), sugar beets ( A. tenuis ), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata ), tomatoes (e. g. A. solani or A. alternata ) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A.
  • tritici anthracnose
  • Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight ( D. maydis ) or Northern leaf blight ( B. zeicola ) on corn, e. g. spot blotch ( B. sorokiniana ) on cereals and e.g. B. oryzae on rice and turfs
  • Blumeria (formerly Elysiphe ) graminis (powdery mildew) on cereals (e. g.
  • Botrytis cinerea (teleomorph: Botryotinia fuckeliana : grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma ) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. ( Cercospora leaf spots) on corn (e.g.
  • Gray leaf spot C. zeae - maydis ), rice, sugar beets (e. g. C. beticola ), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii ) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum : leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris ) spp. (leaf spots) on corn ( C. carbonum ), cereals (e. g.
  • C. sativus anamorph: B. sorokiniana
  • rice e. g. C. miyabeanus , anamorph: H. oryzae
  • Colletotrichum teleomorph: Glomerella
  • spp. anthracnose on cotton (e. g. C. gossypii ), corn (e. g. C. graminicola : Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes : black dot), beans (e. g. C. lindemuthianum ) and soybeans (e. g. C. truncatum or C.
  • 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. D.
  • tritici - repentis tritici - repentis : tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus ) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum ), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits ( E. pyri ), soft fruits ( E. veneta : anthracnose) and vines ( E.
  • ampelina anthracnose
  • Entyloma oryzae leaf smut
  • Epicoccum spp. black mold
  • Erysiphe spp. potowdery mildew
  • sugar beets E. betae
  • vegetables e. g. E. pisi
  • cucurbits e. g. E. cichoracearum
  • cabbages e. g. E. cruciferarum
  • Eutypa lata Eutypa canker or dieback, anamorph: Cytosporina lata , syn.
  • Drechslera teleomorph: Cochliobolus ) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis 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.
  • soybeans e. g. P. manshurica
  • Phakopsora pachyrhizi and P. meibomiae on soybeans
  • Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora )
  • soybeans e. g. P. gregata : stem rot
  • Phoma lingam root and stem rot
  • rape and cabbage P. betae
  • viticola can and leaf spot
  • soybeans e. g. stem rot: P. phaseoli , teleomorph: Diaporthe phaseolorum
  • Physoderma maydis brown spots
  • Phytophthora spp. wilt, root, leaf, fruit and stem root
  • 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.
  • 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.
  • Pseudocercosporella herpotrichoides eyespot, teleomorph: Tapesia yallundae ) on cereals, e. g. wheat or barley
  • Pseudoperonospora downy mildew
  • Pseudopezicula tracheiphila red fire disease or ‘rotbrenner’, anamorph: Phialophora ) on vines
  • Puccinia spp. rusts
  • oryzae (teleomorph: Magnaporthe grisea , rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum ); Ramularia spp., e. g. R. collo - cygni ( Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp.
  • R. solani root and stem rot
  • S. solani silk and stem rot
  • S. solani silk and stem rot
  • S. solani silk blight
  • rice or R. cerealis Rhizoctonia spring blight
  • Rhizopus stolonifer black mold, soft rot
  • strawberries carrots, cabbage, vines and tomatoes
  • Rhynchosporium secalis scald
  • Sarocladium oryzae and S. attenuatum sheath rot) on rice
  • Sclerotinia spp Sclerotinia spp.
  • seed rot or white mold on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum ) and soybeans (e. g. S. rolfsii or S. sclerotiorum ); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici ( Septoria blotch) on wheat and S . (syn. Stagonospora ) nodorum ( Stagonospora blotch) on cereals; Uncinula (syn.
  • Erysiphe ) necator prowdery mildew, anamorph: Oidium tuckeri ) on vines
  • Setospaeria spp. leaf blight
  • corn e. g. S. turcicum , syn. Helminthosporium turcicum
  • turf e. g. S. turcicum , syn. Helminthosporium turcicum
  • Sphaerotheca fuliginea prowdery mildew
  • Spongospora subterranea powdery scab
  • the compounds I and compositions thereof, respectively, may be used for improving the health of a plant.
  • the invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves (“greening effect”)), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e. g. improved plant growth and/or greener leaves (“greening effect”)
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e. g. improved content or composition of certain ingredients
  • the compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
  • the compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
  • An agrochemical composition comprises a fungicidally effective amount of a compound I.
  • the term “effective amount” denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
  • compositions e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g.
  • compositions types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalene, alkylated
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e.g. cellulose, starch
  • fertilizers
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water-soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation are:
  • a compound I and 5-15 wt % wetting agent e.g. alcohol alkoxylates
  • a water-soluble solvent e.g. alcohols
  • a compound I and 1-10 wt % dispersant e. g. polyvinylpyrrolidone
  • organic solvent e.g. cyclohexanone
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e.g. aromatic hydrocarbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 20-40 wt % water-insoluble organic solvent e.g. aromatic hydrocarbon
  • a compound I In an agitated ball mill, 20-60 wt % of a compound I are comminuted with addition of 2-10 wt % dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt % thickener (e.g. xanthan gum) and water ad 100 wt % to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt % binder (e.g. polyvinylalcohol) is added.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • 0.1-2 wt % thickener e.g. xanthan gum
  • water ad 100 wt % to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance.
  • binder e.g. polyvinyl
  • wt % of a compound I are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt % and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • wt % of a compound I are ground in a rotor-stator mill with addition of 1-5 wt % dispersants (e.g. sodium lignosulfonate), 1-3 wt % wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt %. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • a compound I In an agitated ball mill, 5-25 wt % of a compound I are comminuted with addition of 3-10 wt % dispersants (e.g. sodium lignosulfonate), 1-5 wt % thickener (e.g. carboxymethylcellulose) and water ad 100 wt % to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1-5 wt % thickener e.g. carboxymethylcellulose
  • wt % of a compound I are added to 5-30 wt % organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt % surfactant blend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100%. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
  • organic solvent blend e.g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g. alcohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt % of a compound I, 0-40 wt % water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt % acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt % of a compound I according to the invention, 0-40 wt % water insoluble organic solvent (e.g.
  • an isocyanate monomer e.g. diphenylmethene-4,4′-diisocyanate
  • a protective colloid e.g. polyvinyl alcohol
  • the addition of a polyamine results in the formation of polyurea microcapsules.
  • the monomers amount to 1-10 wt %.
  • the wt % relate to the total CS composition.
  • 1-10 wt % of a compound I are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt %.
  • solid carrier e.g. finely divided kaolin
  • a compound I is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt %.
  • solid carrier e.g. silicate
  • Granulation is achieved by extrusion, spray-drying or fluidized bed.
  • organic solvent e.g. aromatic hydrocarbon
  • compositions types i) to xi) may optionally comprise further auxiliaries, such as 0.1-1 wt % bactericides, 5-15 wt % anti-freezing agents, 0.1-1 wt % anti-foaming agents, and 0.1-1 wt % colorants.
  • auxiliaries such as 0.1-1 wt % bactericides, 5-15 wt % anti-freezing agents, 0.1-1 wt % anti-foaming agents, and 0.1-1 wt % colorants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • the compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying compound I and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • compound I or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
  • the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • the present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to L), as described above, and if desired one suitable solvent or solid carrier.
  • agrochemical compositions comprising a mixture of at least one compound I (component 1) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to L), as described above, and if desired one suitable solvent or solid carrier.
  • Those mixtures are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi.
  • a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic mixtures).
  • This can be obtained by applying the compounds I and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or separately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s).
  • the order of application is not essential for working of the present invention.
  • the weight ratio of component 1 and component 2 generally depends from the properties of the active substances used, usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1:3 to 3:1.
  • the weight ratio of component 1 and component 2 depends from the properties of the active substances used, preferably it is in the range of from 1:50 to 50:1 and particularly in the range of from 1:10 to 10:1, and the weight ratio of component 1 and component 3 preferably is in the range of from 1:50 to 50:1 and particularly in the range of from 1:10 to 10:1.
  • mixtures comprising a compound I (component 1) and at least one active substance selected from group A) (component 2) and particularly selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin; famoxadone, fenamidone; benzovindiflupyr, bixafen, boscalid, fluopyram, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, sedaxane; ametoctradin, cyazofamid, fluazinam, fentin salts, such as fentin acetate.
  • azoxystrobin dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin
  • mixtures comprising a compound of formula I (component 1) and at least one active substance selected from group B) (component 2) and particularly selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, fenarimol, triforine; dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine; fenhexamid.
  • mixtures comprising a compound of formula I (component 1) and at least one active substance selected from group C) (component 2) and particularly selected from metalaxyl, (metalaxyl-M) mefenoxam, ofurace.
  • mixtures comprising a compound of formula I (component 1) and at least one active substance selected from group D) (component 2) and particularly selected from benomyl, carbendazim, thiophanate-methyl, ethaboxam, fluopicolide, zoxamide, metrafenone, pyriofenone.
  • mixtures comprising a compound I (component 1) and at least one active substance selected from group E) (component 2) and particularly selected from cyprodinil, mepanipyrim, pyrimethanil.
  • mixtures comprising a compound I (component 1) and at least one active substance selected from group F) (component 2) and particularly selected from iprodione, fludioxonil, vinclozolin, quinoxyfen.
  • mixtures comprising a compound I (component 1) and at least one active substance selected from group G) (component 2) and particularly selected from dimethomorph, flumorph, iprovalicarb, benthiavalicarb, mandipropamid, propamocarb.
  • mixtures comprising a compound I (component 1) and at least one active substance selected from group H) (component 2) and particularly selected from copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, mancozeb, metiram, propineb, thiram, captafol, folpet, chlorothalonil, dichlofluanid, dithianon.
  • mixtures comprising a compound I (component 1) and at least one active substance selected from group I) (component 2) and particularly selected from carpropamid and fenoxanil.
  • mixtures comprising a compound I (component 1) and at least one active substance selected from group J) (component 2) and particularly selected from acibenzolar-S-methyl, probenazole, tiadinil, fosetyl, fosetyl-aluminium, H 3 PO 3 and salts thereof.
  • mixtures comprising a compound I (component 1) and at least one active substance selected from group K) (component 2) and particularly selected from cymoxanil, proquinazid and N-methyl-2- ⁇ 1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl]-piperidin-4-yl ⁇ -N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide.
  • mixtures comprising a compound 1 (component 1) and at least one active substance selected from group L) (component 2) and particularly selected from Bacillus subtilis strain NRRL No. B-21661, Bacillus pumilus strain NRRL No. B-30087 and Ulocladium oudemansii.
  • the present invention furthermore relates to compositions comprising one compound I (component 1) and one further active substance (component 2), which further active substance is selected from the column “Component 2” of the lines B-1 to B-369 of Table B.
  • a further embodiment relates to the compositions B-1 to B-369 listed in Table B, where a row of Table B corresponds in each case to a fungicidal composition comprising one of the in the present specification individualized compounds of formula I (component 1) and the respective further active substance from groups A) to O) (component 2) stated in the row in question.
  • the compositions described comprise the active substances in synergistically effective amounts.
  • B-21661 B-267 one individualized compound I Bacillus pumilus NRRL No. B-30087 B-268 one individualized compound I Ulocladium oudemansii B-269 one individualized compound I Carbaryl B-270 one individualized compound I Carbofuran B-271 one individualized compound I Carbosulfan B-272 one individualized compound I Methomylthiodicarb B-273 one individualized compound I Bifenthrin B-274 one individualized compound I Cyfluthrin B-275 one individualized compound I Cypermethrin B-276 one individualized compound I alpha-Cypermethrin B-277 one individualized compound I zeta-Cypermethrin B-278 one individualized compound I Deltamethrin B-279 one individualized compound I Esfenvalerate B-280 one individualized compound I Lambda-cyhalothrin B-281 one individualized compound I Permethrin B-282 one individualized compound I Tefluthrin B
  • component 2 The active substances referred to as component 2, their preparation and their activity against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available.
  • the compounds described by IUPAC nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci.
  • the mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient by usual means, e. g. by the means given for the compositions of compounds I.
  • the mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, it is referred to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds I, respectively.
  • R 6 CH 3 I-212 phenyl ring* R3-98 R4-7 Y-1 151° C.
  • R 6 CH 3 I-213 phenyl ring* R3-130 R4-7 Y-4
  • R 6 CH 3 I-214 phenyl ring* R3-131 R4-7 Y-4 139-142° C.
  • R 6 CH 3 I-215 phenyl ring* R3-132 R4-7 Y-4 58-63° C.
  • R 6 CH 3 I-216 phenyl ring* R3-133 R4-7 Y-1 111-113° C.
  • R 6 CH 3 I-217 phenyl ring* R3-65 R4-7 Y-1 78-88° C.
  • R 6 CH 3 I-218 phenyl ring* R3-60 R4-7 Y-1 83-88° C.
  • R 6 CH 3 I-219 phenyl ring* R3-67 R4-7 Y-1 87-89° C.
  • R 6 CH 3 I-220 phenyl ring* R3-62 R4-7 Y-1 82-88° C.
  • R 6 CH 3 I-221 phenyl ring* R3-134 R4-7 Y-1 92-98° C.
  • R 6 CH 3 I-222 phenyl ring* R3-135 R4-7 Y-1 141-145° C.
  • R 6 CH 3 I-223 phenyl ring* R3-64 R4-7 Y-1 88-91° C.
  • R 6 CH 3 I-224 phenyl ring* R3-59 R4-7 Y-1 82-86° C.
  • R 6 CH 3 I-225 phenyl ring* R3-63 R4-7 Y-1 64-70° C.
  • R 6 CH 3 I-226 phenyl ring* R3-136 R4-7 Y-1 101-108° C.
  • R 6 CH 3 I-227 phenyl ring* R3-137 R4-7 Y-1 98-102° C.
  • R 6 CH 3 I-228 phenyl ring* R3-138 R4-7 Y-1 71-75° C.
  • R 6 CH 3 I-229 phenyl ring* R3-139 R4-7 Y-7 72-74° C.
  • R 6 CH 3 I-252 phenyl ring* R3-151 R4-7 Y-1 102-104° C.
  • R 6 Ethyl I-253 phenyl ring* R3-1 R4-7 Y-1 96-97° C.
  • R 6 Ethyl I-255 phenyl ring* R3-68 R4-7 Y-1
  • Rt 4.239 min
  • R 6 Ethyl I-256 phenyl ring* R3-146 R4-7 Y-1
  • R t 4.176 min
  • I-294 CH 3 H R3-177 R4-1 O Y-1 ⁇ 1.93 (s); 3.20 (m); 3.28 (m); 3.83 (s); 3.90 (m); 4.05 (s); 4.42 (m); 4.50 (m); 5.88 (m); 5.94 (s); 6.83 (m); 7.25 (m); 7.50 (s) I-295 CH 3 H R3-39 R4-1 NH Y-1 142° C.
  • I-303 CH 3 H R3-33 R4-1 O Y-1 ⁇ 1.95 (s); 3.83 (s); 4.05 (s); 4.65 (m); 5.95 (m); 7.37 (m); 7.57 (m); 8.27 (s)
  • I-304 CH 3 H R3-54 R4-1 O Y-1 ⁇ 1.25 (m); 1.95 (s); 2.68 (m); 3.83 (s); 4.05 (s); 4.65 (m); 5.95 (m); 7.30 (m); 7.51 (m); 8.20 (s) I-305 CH 3 H R3-33 R4-1 NH Y-1 126° C. I-306 CH 3 H R3-54 R4-1 NH Y-1 128° C.
  • the active substances were formulated separately as a stock solution in dimethyl sulfoxide (DMSO) at a concentration of 10 000 ppm.
  • DMSO dimethyl sulfoxide
  • the antifungal activity was determined by measuring the turbidity of a culture in 96-well microplates in the presence of test compounds. Fungal growth was measured by recording the optical density at 620 nm every 15 h for 150 h. The relative antifungal activity was calculated by comparison of the effect of the test compounds with the effect of a DMSO control and a standard fungicide.
  • IC 50 -values concentration of test compound resulting in 50% inhibition of fungal growth
  • concentration of test compound resulting in 50% inhibition of fungal growth were calculated from the resulting dose-response for each compound and strain.
  • the initial concentration of the test compounds and the 10 steps of dilution (1:4 each) allowed IC 50 -values from 0.001 to 100 ⁇ mol/l ( ⁇ M) to be assessed.
  • While commercial strobilurine type fungicides are do not show any activity against the resistant Septoria strain, containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors (G143A) while being active against sensitive wild type strains, compounds I have been active against both, the resistant and the wild-type strains.
  • the resistance factor ratio (RF) calculated from the IC50 values determined for both Septoria strains was below 30 for the compounds I according to the invention.
  • resistance factor ratios for commercial strobilurine type compounds are in most cases greater than 100 and usually greater than several hundreds (for details see e.g. FRAC, Mutations associated with QoI-resistance, December 2006; http://frac.info/frac/work/Mutations%20associated%20with%20QoI%20resistance.pdf and citations cited therein).
  • Compound I-6 was used as 50 g/l EC formulation. Pyraclostrobin was used as commercial product HEADLINE.
  • the spray solutions were prepared in several steps:
  • the stock solution was prepared as follows: 1.26 ml of a 1:1 mixture of cyclohexanone and dimethylsulfoxide was added to 8.4 mg of active ingredient. Next, 40.74 ml of a mixture of water, acetone (10%), the emulsifier Wettol (0.1%) and the wetting agent Silwet (0.05%) was added. This stock solution was then further diluted with the described solvent-emulsifier-water mixture to the desired concentrations.
  • Wheat plants were grown in pots. These plants were sprayed to run-off with an aqueous suspension, containing the desired concentration of active ingredient. The next day, the treated plants were inoculated with an aqueous suspension of Septoria tritici . After inoculation, the trial plants were covered with a lid and immediately transferred to a chamber with a relative humidity of about 83 to 85% and 19.5 to 20° C. After 4 days the lid was removed. Altogether, the trial plants were cultivated for about 28 days in that greenhouse chamber. The extent of fungal attack on the leaves was then visually assessed as % diseased leaf area.
  • Cytochrome b was isolated from the structure of the complex and treated with the Schrödinger Protein Preparation Wizard (Schrödinger Suite 2009 Protein Preparation Wizard; Epik version 2.0, Schrödinger, LLC, New York, N.Y., 2009; Impact version 5.5, Schrödinger, LLC, New York, N.Y., 2009, Prime version 2.1, Schrödinger, LLC, New York, N.Y., 2009).
  • the model of the G143A mutant was generated by changing a hydrogen in Glycine 143 of the wild-type model into a methyl group, thereby generating S-Alanine, using Schrödinger Maestro.
  • Amino acids in a sphere of 5 ⁇ around the co-crystallized molecule of azoxystrobin were energy-minimized using Schrödinger MacroModel (version 9.7, Schrödinger, LLC, New York, N.Y., 2009).
  • the docked ligands were transferred to the G143A binding site model keeping the coordinates from docking into the wild-type model. Thereby, complexes between the G143A binding site and ligands were formed. Those were used as starting structures for the following energy minimization using Schrödinger MacroModel. During these simulations, only the ligand was allowed to move freely, the protein was considered “frozen”. The poses generated by this procedure were considered as the relaxed state of the inhibitors after introduction of the G143A mutation.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Furan Compounds (AREA)
  • Pretreatment Of Seeds And Plants (AREA)

Abstract

The present invention relates to the use of strobilurine type compounds of formula I and the N-oxides and the salts thereof for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, and to methods for combating such fungi. The invention also relates to novel compounds, processes for preparing these compounds, to compositions comprising at least one such compound, to plant health applications, and to seeds coated with at least one such compound.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a continuation of U.S. application Ser. No. 15/054,828, filed Feb. 26, 2016, the entire contents of which is hereby incorporated herein by reference. U.S. application Ser. No. 15/054,828, is a continuation of U.S. application Ser. No. 14/364,532, filed Jun. 11, 2014 (now U.S. Pat. No. 9,271,501), the entire contents of which is hereby incorporated herein by reference. U.S. application Ser. No. 14/364,532, is the National Stage application of International Application No. PCT/EP2012/074586, filed Dec. 6, 2012, the entire contents of which is hereby incorporated herein by reference. U.S. application Ser. No. 14/364,532, also claims priority under 35 U.S.C. § 119 to European Patent Application No. 11195032.5, filed Dec. 21, 2011, and to European Patent Application No. 12190109.4, filed Oct. 26, 2012, the entire contents of each are hereby incorporated herein by reference.
    • DESCRIPTION
  • The present invention relates to the use of strobilurine type compounds of formula I and the N-oxides and the salts thereof for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, and to methods for combating such fungi. The invention also relates to novel compounds, processes for preparing these compounds, to compositions comprising at least one such compound, to plant health applications, and to seeds coated with at least one such compound.
  • Qo inhibitor fungicides, often referred to as strobilurin-type fungicides (Sauter 2007: Chapter 13.2. Strobilurins and other complex III inhibitors. In: Krämer, W.; Schirmer, U. (Ed.)—Modern Crop Protection Compounds. Volume 2. Wiley-VCH Verlag 457-495), are conventionally used to control a number of fungal pathogens in crops. Qo inhibitors typically work by inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bc1 complex (electron transport complex III) in mitochondria. Said oxidation center is located on the outer side of the inner mitochrondrial membrane. A prime example of the use of Qo inhibitors includes the use of, for example, strobilurins on wheat for the control of Septoria tritici (also known as Mycosphaerella graminicola), which is the cause of wheat leaf blotch. Unfortunately, widespread use of such Qo inhibitors has resulted in the selection of mutant pathogens which are resistant to such Qo inhibitors (Gisi et al., Pest Manag Sci 56, 833-841, (2000). Resistance to Qo inhibitors has been detected in several phytopathogenic fungi such as Blumeria graminis, Mycosphaerella fijiensis, Pseudoperonspora cubensis or Venturia inaequalis. Although several resistance mechanisms have been detected meanwhile (e.g. Jabs et al. Phytomedizin 31, 15-16 (2001); Olaya et al., Pestic Sci 54, 230-236 (1998), the major part of resistance to Qo inhibitors in agricultural uses has been attributed to pathogens containing a single amino acid residue substitution G143A in the cytochrome b gene for their cytochrome bc1 complex, the target protein of Qo inhibitors. See, for example, Lucas, Pestic Outlook 14(6), 268-70 (2003); and Fraaije et al., Phytopathol 95(8), 933-41 (2005), (which both are expressly incorporated by reference herein). Thus, new methods and compositions are desirable for controlling pathogen induced diseases in crops comprising plants subjected to pathogens that are resistant to Qo inhibitors. Furthermore, in many cases, in particular at low application rates, the fungicidal activity of the known fungicidal strobilurin analogue compounds is unsatisfactory, especially in case that a high proportion of the fungal pathogens contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors. Based on this, it was also an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic harmful fungi.
  • “Qo inhibitor,” as used herein, includes any substance that is capable of diminishing and/or inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bc1 complex in mitochondria. The oxidation center is typically located on the outer side of the inner mitochrondrial membrane.
  • From WO 2009/155095, the use of a Qi inhibitor UK2A of formula
  • Figure US20180360041A1-20181220-C00001
  • is known for combating phytopathogenic fungi that are resistant to Qo inhibitors. Qi inhibitors typically work by inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bcl complex in mitochondria, the said oxidation center being located on the inner side of the inner mitochrondrial membrane.
  • The strobilurin-analogue compounds according to the present invention differ from those described in the abovemention publication by the specific formula I and by inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bcl complex in mitochondria which defines them as Qo inhibitors. Besides the strobilurin analogue-specific structural elements R4, these compounds contain two specific carbon atoms bound by a double bond wherein the groups R1 and R2 are cis-oriented or the R1 and R2 together with the abovementioned two carbon atoms linking them form a phenyl ring if R4 is 4-methyl-1,4-dihydro-tetrazol-5-on-1-yl.
    • BRIEF DESCRIPTION OF THE INVENTION
  • Accordingly, the present invention relates to the use of compounds of formula I
  • Figure US20180360041A1-20181220-C00002
  • wherein:
    • R1, R2 independently of each other are hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl, wherein the groups R1 and R2 are cis-oriented, or
      • R1 and R2 together with the two carbon atoms linking them form a phenyl ring provided
      • that R4 is 4-methyl-1,4-dihydro-tetrazol-5-one-1-yl (formula R4-7), and
        • wherein the aliphatic moieties of R1 and/or R2 or the abovementioned phenyl ring may carry 1, 2, 3 or up to the maximum number of identical or different groups Ra which independently of one another are selected from:
      • Ra halogen, CN, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-haloalkoxy;
    • Y is a direct bond or a divalent group selected from —OCH2—, —CH2—, —CH2CH2—, —C(Z)═N—O—CH2—, —CHZ—C(Z)═N—O—CH2—, —O—N═C(Z)—C(Z)═N—O—CH2—, —C(═O)—C(Z)═N—O—CH2— and —C(═N—O—Z)—C(Z)═N—O—CH2—,
      • where the bond depicted on the left side of the divalent group Y is attached to R3, and the bond depicted on the right side is attached to the carbon atom being substituted by R2, and
      • Z, which may be the same or different to any other Z, is hydrogen, C1-C4-alkyl or C1-C4-haloalkyl;
    • R3 is phenyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl wherein the ring member atoms of the heterocyclyl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S;
      • wherein the cyclic groups R3 may carry 1, 2, 3, 4 or up to the maximum possible number of identical or different groups Rb which independently of one another are selected from:
      • Rb, which may be the same or different to any other Rb, is amino, halogen, hydroxyl, oxo, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C2-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C6-alkoxyimino-C1-C4alkyl, C2-C6-alkenyloxyimino-C1-C4-alkyl, C2-C6-alkynyloxyimino-C1-C4-alkyl, C1-C4-alkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyloxy, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of N, O and S as ring members; and wherein the aforementioned phenyl and heterocyclyl groups Rb are attached via a direct bond, an oxygen or sulfur atom, and
      • two radicals Rb that are bound to adjacent ring member atoms of the cyclic group R3 may form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic cycle, which may be a carbocycle or heterocycle, wherein the ring member atoms of the heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S,
      • and
      • where the aliphatic or cyclic groups Rb for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rc:
      • Rc, which may be the same or different to any other Rc, is halogen, hydroxyl, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C8-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C6-alkoxyimino-C1-C4-alkyl, C2-C6-alkenyloxyimino-C1-C4-alkyl, C2-C6-alkynyloxyimino-C1-C4-alkyl, C1-C6-alkoxyimino-, C2-C6-alkenyloxyimino-, C2-C6-alkynyloxyimino-, C2-C6-haloalkenyloxyimino-, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, phenyl or a 5-membered saturated, partially unsaturated or aromatic heterocyclyl which, in addition to carbon atoms, contains one to three heteroatoms from the group consisting of N, O and S as ring members; wherein the aforementioned cyclic groups Rc are attached via a direct bond, an oxygen or sulfur atom, and where the aliphatic or cyclic groups Rc for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rd:
      • Rd, which may be the same or different to any other Rd, is halogen, C1-C4-alkyl or C1-C4-haloalkyl;
      • or
        R3 is —CRA═N—O—RB, wherein
      • RA is amino, hydroxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C2-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C4-alkoxyimino-C1-C4-alkyl, C1-C4-alkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyloxy, phenyl, phenyl-C1-C4-alkyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; and wherein the aforementioned cyclic RA are attached via a direct bond, an oxygen or sulfur atom;
      • RB is C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C1-C4-alkoxyimino-C1-C4-alkyl, C1-C4-alkoxycarbonyl, phenyl, phenyl-C1-C4-alkyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members;
        • where the aliphatic or cyclic groups RA and/or RB for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Re:
        • Re, which may be the same or different to any other Re, is halogen, hydroxyl, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C8-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
          R4 is a monovalent group selected from formulae R4-1 to R4-7
  • Figure US20180360041A1-20181220-C00003
      • wherein the jagged line defines the point of attachment, and
      • X is a direct bond or a divalent group CH2, 0 or NH,
      • R5 is C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or C3-C6-cycloalkyl,
      • R6 is C1-C4-alkyl or C1-C4-haloalkyl;
        and the N-oxides and the agriculturally acceptable salts thereof, for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors.
  • Furthermore, the present invention also relates to methods for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors using the abovementioned compounds of formula I.
  • Certain strobilurin type compounds of formula I, wherein R4 is 1-methoxycarbonyl-2-methoxy-ethen-1-yl (defined as R4-2 herein, wherein X is O) and R1 is CF3, are mentioned in WO 1998/021174: (E)-2-[1-methoxy-meth-(E)-ylidene]-5-(4-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester (CAS No. 207852-99-1); (E)-2-[1-methoxy-meth-(E)-ylidene]-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester (207853-00-7); (E)-2-[1-methoxy-meth-(E)-ylidene]-4-methyl-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester; and (E)-5,5,5-trifluoro-2-[1-methoxy-meth-(E)-ylidene]-3-methyl-4-(4-phenoxy-phenoxymethyl)-pent-3-enoic acid methyl ester. However, it is not mentioned that the strobilurine type compounds inhibit fungal pathogens containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors. II
  • Further, preparation of the compound (2E,3Z)-2-(ethylidene)-5-phenyl-3-pentenoic acid methyl ester (CAS-No. 681026-20-0) has been described in J Organomet Chem 689, 575-584 (2004).
  • Further, certain strobilurin type compounds, wherein R1 and R2 together with the two carbon atoms linking them form a phenyl ring and wherein R4 is 1-methyl-1,4-dihydro-tetrazole-5-one-4-yl (R4-7) are known inter alia from WO 1996/036229, WO 1999/046246 and DE 199 00 571 A1.
  • The compounds according to the present invention differ from those described in the abovementioned publications that R1 and R2 do not form with the two carbon atoms linking them a phenyl ring, and that (E)-2-[1-methoxy-meth-(E)-ylidene]-5-(4-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester (207852-99-1); (E)-2-[1-methoxy-meth-(E)-ylidene]-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester (207853-00-7); (E)-2-[1-methoxy-meth-(E)-ylidene]-4-methyl-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester; (E)-5,5,5-trifluoro-2-[1-methoxy-meth-(E)-ylidene]-3-methyl-4-(4-phenoxy-phenoxymethyl)-pent-3-enoic acid methyl ester; and (2E,3Z)-2-(ethylidene)-5-phenyl-3-pentenoic acid methyl ester (CAS-No. 681026-20-0) are excluded.
  • Therefore, according to a second aspect, the invention provides compounds of formula I which are represented by formula I
  • Figure US20180360041A1-20181220-C00004
  • wherein:
    • R1, R2 independently of each other are hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl,
      • wherein the groups R1 and R2 are cis-oriented,
      • wherein the aliphatic moieties of R1 and/or R2 may carry 1, 2, 3 or up to the maximum number of identical or different groups Ra which independently of one another are selected from:
      • Ra halogen, CN, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-haloalkoxy;
    • Y is a direct bond or a divalent group selected from —OCH2—, —CH2—, —CH2CH2—, —C(Z)═N—O—CH2—, —CHZ—C(Z)═N—O—CH2—, —O—N═C(Z)—C(Z)═N—O—CH2—, —C(═O)—C(Z)═N—O—CH2— and —C(═N—O—Z)—C(Z)═N—O—CH2—,
      • where the bond depicted on the left side of the divalent group Y is attached to R3, and the bond depicted on the right side is attached to the carbon atom being substituted by R2, and
      • Z, which may be the same or different to any other Z, is C1-C4-alkyl or C1-C4-haloalkyl;
    • R3 is phenyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl wherein the ring member atoms of the heterocyclyl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S;
      • wherein the cyclic groups R3 may carry 1, 2, 3, 4 or up to the maximum possible number of identical or different groups Rb which independently of one another are selected from:
      • Rb, which may be the same or different to any other Rb, is amino, halogen, hydroxyl, oxo, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4alkoxy, C1-C4-haloalkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C2-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C6-alkoxyimino-C1-C4-alkyl, C2-C6-alkenyloxyimino-C1-C4-alkyl, C2-C6-alkynyloxyimino-C1-C4-alkyl, C1-C4-alkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyloxy, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl or which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of N, O and S as ring members; and wherein the aforementioned phenyl and heterocyclyl groups Rb are attached via a direct bond, an oxygen or sulfur atom;
        • and
        • two radicals Rb that are bound to adjacent ring member atoms of the cyclic group R3 may form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic cycle, which may be a carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and where the aliphatic or cyclic groups Rb for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rc:
        • Rc, which may be the same or different to any other Rc, is halogen, hydroxyl, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C8-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C6-alkoxyimino-C1-C4-alkyl, C2-C6-alkenyloxyimino-C1-C4-alkyl, C2-C6-alkynyloxyimino-C1-C4-alkyl, C1-C4-alkoxyimino-C1-C4-alkyl, C1-C6-alkoxyimino-, C2-C6-alkenyloxyimino-, C2-C6-alkynyloxyimino-, C2-C6-haloalkenyloxyimino-, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, phenyl or a 5-membered saturated, partially unsaturated or aromatic heterocyclyl which, in addition to carbon atoms, contains one to three heteroatoms from the group consisting of N, O and S as ring members; wherein the aforementioned cyclic groups Rc are attached via a direct bond, an oxygen or sulfur atom and where the aliphatic or cyclic groups Rc for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rd:
        • Rd, which may be the same or different to any other Rd, is halogen, C1-C4-alkyl or C1-C4-haloalkyl;
      • or
        R3 is —CRA═N—O—RB, wherein
      • RA is amino, hydroxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C2-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C4-alkoxyimino-C1-C4-alkyl, C1-C4-alkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyloxy, phenyl, phenyl-C1-C4-alkyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; and wherein the aforementioned cyclic RA are attached via a direct bond, an oxygen or sulfur atom;
      • RB is C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C1-C4-alkoxyimino-C1-C4-alkyl, C1-C4-alkoxycarbonyl, phenyl, phenyl-C1-C4-alkyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members;
        • where the aliphatic or cyclic groups RA and/or RB for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Re:
        • Re, which may be the same or different to any other Re, is halogen, hydroxyl, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C8-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
          R4 is a monovalent group selected from formulae R4-1 to R4-7
  • Figure US20180360041A1-20181220-C00005
      • wherein the jagged line defines the point of attachment, and where
      • X is a divalent group O or NH,
      • R5 is C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or C3-C6-cycloalkyl,
      • R6 is C1-C4-alkyl or C1-C4-haloalkyl;
        and the N-oxides and the agriculturally acceptable salts thereof, except for (E)-2-[1-methoxy-meth-(E)-ylidene]-5-(4-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester (207852-99-1), (E)-2-[1-methoxy-meth-(E)-ylidene]-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester (207853-00-7); (E)-2-[1-methoxy-meth-(E)-ylidene]-4-methyl-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic acid methyl ester, (E)-5,5,5-trifluoro-2-[1-methoxy-meth-(E)-ylidene]-3-methyl-4-(4-phenoxy-phenoxymethyl)-pent-3-enoic acid methyl ester, and
        (2E,3Z)-2-(ethylidene)-5-phenyl-3-pentenoic acid methyl ester (CAS-No. 681026-20-0).
    BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1: The commercially available strobilurin analogue compound Pyraclostrobin modelled into an artificial cytochrome bc1 complex Qo-binding site displays steric clash of the phenyl ring with the 143A methyl group as indicated by arrow in the upper right part of the picture (see left picture). Compound I-6 according to the present invention does not show a steric clash (see right picture).
    •  DETAILED DESCRIPTION OF THE INVENTION
  • The term “compounds I” refers to compounds of formula I. Likewise, this terminology applies to all sub-formulae, e. g. “compounds I.2” refers to compounds of formula I.2 or “compounds V” refers to compounds of formula V, etc.
  • The compounds I can be obtained by various routes in analogy to prior art processes known (e.g. WO 1998/021174, J Organomet Chem 689, 575-584 (2004), WO 1996/036229) and, advantageously, by the synthesis shown in the following schemes and in the experimental part of this application.
  • A suitable method to prepare compounds I is illustrated in scheme 1. It starts with the reduction of an acetylene compound II with a reducing agent like lithium aluminium hydride preferably in the presence of a solvent. Suitable solvents are inert against the reducing agent used and preferably selected from cyclic or aliphatic ethers like diethyl ether, tetrahydrofurane (THF), 1,4-dioxane, and methyl-tert.-butyl ether (MTBE). The reaction temperature can be between −40° C. and 100° C., preferably −20 to 60° C. After a reduced intermediate has been formed, a tin compound of formula III, wherein Alk defines a suitable alkyl residue like methyl, ethyl, n-propyl, or n-butyl and wherein L is a leaving group such as halogen, ethoxy and methoxy, in particular methoxy, is added. The resulting intermediate IV is a stable compound which can be isolated and purified with the usual methods (for example extraction and chromatography).
  • Compound IV is further reacted with compound V to yield the intermediate VI applying the usual methods for coupling aliphatic alcohols with hydroxyl compounds IV. The Mitsonobu reaction has proven especially useful.
  • Compound VI is then coupled with compound VII, wherein LG is a leaving group, preferably being halogen (except fluoro) or a sulfonyloxy group such as triflate, preferably in the presence of a suitable catalyst such as known transition metal catalysts, more preferably palladium catalysts, wherein the ligand may be trifurylphoshine, triphenyl phosphine, tritolyl phosphine or bidentate phosphine ligands. The. Copper compounds, such as CuI2 can be added to improve the reaction. A wide variety of solvents is possible here, with THF, 1,4-dioxane and amides like dimethylformamide (DMF) being preferred. The reaction temperatures can be −20 to 150° C., preferably 20 to 120° C.
  • The resulting compounds I, wherein Y is —OCH2— and R2 is H, can be further modified. For example, if R4 contains an ester group, VIII can be transformed into a methyl amide by reaction with methyl amine.
  • Figure US20180360041A1-20181220-C00006
  • Another general method to prepare compounds I is illustrated in scheme 2. The starting materials VIII are either known or can be prepared analogous to known compounds. The Wittig-Homer reaction of compounds VIII with compounds IX illustrated here (see also Tetrahedron Lett. 1988, 29, 3361) can be replaced by the Wittig reaction if this results in better yields. These reactions as well as the reaction conditions are well known. A specific problem is the E/Z-ratio in the newly formed double bond. The desired isomer is usually accompanied by some undesired isomer, which has to be removed by purification known in the art (e. g. chromatography, distillation, crystallization, etc.).
  • Figure US20180360041A1-20181220-C00007
  • A route to compounds I, wherein R4 is of formula R4-4, is illustrated in scheme 3. The compound X can be obtained for example from compound VI by direct reaction with iodine. The iodine in compounds X may be replaced by other suitable leaving groups, for example by bromine, chlorine or triflate. The sodium atom in the salt VII can be replaced by other suitable metal atoms, for example potassium, lithium, magnesium, calcium, etc. The coupling reaction of X and XI is performed preferably in the presence of a transition metal catalyst being preferably copper in the presence of a nitrogen containing ligand system (see e.g.: Tetrahedron Lett 2008, 49 (26), 4196-4199; Org Lett. 2004, 6 (11), 1809-1812).
  • Figure US20180360041A1-20181220-C00008
  • If individual compounds I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds I.
  • If the synthesis yields mixtures of isomers in the case of oximes, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.
  • In the definitions of the variables given above, collective terms are used which are generally representative for the substituents in question. The term “Cn-Cm” indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
  • The term “halogen” refers to fluorine, chlorine, bromine and iodine.
  • The term “C1-C6-alkyl” refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl (isobutyl), 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methyl pentyl, 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. Likewise, the term “C1-C4-alkyl” refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms.
  • The term “C1-C4-haloalkyl” refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms (as defined above), wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH2—C2F5, CF2—C2F5, CF(CF3)2, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Likewise, the term “C1-C6-haloalkyl” refers to a straight-chained or branched alkyl group having 1 to 6 carbon atoms.
  • The term “C1-C6-alkoxy” refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkyl group, e.g. OCH3, OCH2CH3, O(CH2)2CH3, 1-methylethoxy, O(CH2)3CH3, 1-methyl¬propoxy, 2-methylpropoxy or 1,1-dimethylethoxy, O(CH2)4CH3 or O(CH2)5CH3. Likewise, the term “C1-C4-alkoxy” refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms which is bonded via an oxygen, at any position in the alkyl group.
  • The term “C1-C4-haloalkoxy” refers to a C1-C4-alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, for example, OCH2F, OCHF2, OCF3, OCH2Cl, OCHCl2, OCCl3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloro¬ethoxy, 0C2F5, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoro¬propoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromo¬propoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2—C2F5, OCF2—C2F5, 1-(CH2F)-2-fluoroethoxy, 1-(CH2Cl)-2-chloroethoxy, 1-(CH2Br)-2-bromo¬ethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy. Likewise, the term “C1-C6-haloalkoxy” refers to a C1-C6-alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above.
  • The term “C1-C4-alkoxy-C1-C4-alkyl” refers to alkyl having 1 to 4 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a C1-C4-alkoxy group. Likewise, the term “C1-C6-alkoxy-C1-C6-alkyl” refers to alkyl having 1 to 6 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a C1-C6-alkoxy group.
  • The term “C1-C4-alkylamino” refers to an amino radical carrying one C1-C4-alkyl group as substituent, e.g. methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1,1-dimethylethylamino and the like. Likewise, the term “C1-C6-alkylamino” refers to an amino radical carrying one C1-C6-alkyl group as substituent.
  • The term “di(C1-C4-alkyl)amino” refers to an amino radical carrying two identical or different C1-C4-alkyl groups as substituents, e. g. dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-N methylamino, N-(n-butyl)-N-methylamino, N-(2-butyl)-N methylamino, N-(isobutyl)-N-methylamino, and the like. Likewise, the term “di(C1-C6-alkyl)amino” refers to an amino radical carrying two identical or different C1-C6-alkyl groups as substituents.
  • The term “C1-C4-alkoxyimino” refers to a divalent imino radical (C1-C4-alkyl-O—N═) carrying one C1-C4-alkoxy group as substituent, e.g. methylimino, ethylimino, propylimino, 1-methylethylimino, butylimino, 1-methylpropylimino, 2-methylpropylimino, 1,1-dimethylethylimino and the like.
  • The term “C1-C6-alkoxyimino-C1-C4-alkyl” refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein two hydrogen atoms of one carbon atom of the alkyl radical are replaced by a divalent C1-C6-alkoxyimino radical (C1-C6-alkyl-O—N═) as defined above.
  • The term “C2-C6-alkenyloxyimino-C1-C4-alkyl” refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein two hydrogen atoms of one carbon atom of the alkyl radical are replaced by a divalent C2-C6-alkenyloxyimino radical (C2-C6-alkenyl-O—N═).
  • The term “C2-C6-alkynyloxyimino-C1-C4-alkyl” refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein two hydrogen atoms of one carbon atom of the alkyl radical are replaced by a divalent C2-C6-alkynyloxyimino radical (C2-C6-alkynyl-O—N═).
  • The term “C1-C4-alkylcarbonyl” refers to a C1-C4-alkyl radical which is attached via a carbonyl group. The term “(C1-C6-alkoxy)carbonyl” refers to a C1-C6-alkoxy radical which is attached via a carbonyl group.
  • The term “C1-C6-alkylaminocarbonyl” refers to a C1-C6-alkylamino radical which is attached via a carbonyl group. Likewise, the term “di(C1-C6-alkyl)aminocarbonyl” refers to a di(C1-C6)alkylamino radical which is attached via a carbonyl group.
  • The term “C2-C4-alkenyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and a double bond in any position, e.g. ethenyl, 1-propenyl, 2-propenyl (allyl), 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl. Likewise, the term “C2-C6-alkenyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position.
  • The term “C2-C4-alkynyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and containing at least one triple bond, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl. Likewise, the term “C2-C6-alkynyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and at least one triple bond.
  • The term “C3-C6-cycloalkyl” refers to monocyclic, bicyclic, saturated hydrocarbon radicals having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Likewise, the term “C3-C6-cycloalkenyl” refers to unsaturated hydrocarbon radicals having 3 to 6 carbon ring members and a double bond in any position, such as cyclopropenyl, cyclobutenyl, cyclopentenyl or cyclohexenyl.
  • The term “C3-C6-cycloalkyl-C1-C4-alkyl” refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical having 3 to 6 carbon atoms.
  • The term “phenyl-C1-C4-alkyl” refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a phenyl radical.
  • Agriculturally acceptable salts of compounds I encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four C1-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • The compounds of formula I can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
  • Depending on the substitution pattern, the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or diastereomers and their mixtures are subject matter of the present invention.
  • In respect of the variables, the embodiments of the intermediates correspond to the embodiments of the compounds I.
  • Preference is given to those compounds I and where applicable also to compounds of all sub-formulae provided herein, e. g. formulae I.1 and I.2, and to the intermediates such as compounds II, III, IV and V, wherein the substituents and variables (such as k, R1, R2, R3, R4, R5, R6, X, Y, Z, RA, RB, Ra, Rb Rc, Rd and Re) have independently of each other or more preferably in combination (any possible combination of 2 or more substituents as defined herein) the following meanings:
  • Preference is also given to the uses, methods, mixtures and compositions, wherein the definitions (such as phytopathogenic fungi, treatments, crops, compounds II, further active ingredients, solvents, solid carriers) have independently of each other or more preferably in combination the following meanings and even more preferably in combination (any possible combination of 2 or more definitions as provided herein) with the preferred meanings of compounds I herein:
  • According to one embodiment of the invention, the invention also relates to a method for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, comprising: treating the phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors with an effective amount of at least one compound I, or a composition comprising it thereof.
  • The term “phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors” is to be understood that at least 10% of the fungal isolates to be controlled contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, more preferably at least 30%, even more preferably at least 50%, and most preferably at least 75% of the fungi, in particular between 90 and 100%.
  • It has been observed under field conditions that populations of phytopathogenic fungi apparently consisting of non-resistant strains can readily develop resistance. The compounds can be applied under such conditions, too, in order to prevent the formation of resistance and the spread of resistant strains altogether. In this regard it is useful that they have strong activity against non-resistant phytopathogenic fungi also.
  • According to another embodiment, the method for combating phytopathogenic fungi, comprises: a) identifying the phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi as defined herein, and b) treating said fungi or the materials, plants, the soil or seeds with an effective amount of at least one compound I, or a composition comprising it thereof.
  • According to another embodiment of the invention, the invention also relates to a method for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, comprising: treating the phytopathogenic fungi whereof at least 10% contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors with an effective amount of at least one compound I, or a composition comprising it thereof; more preferably at least 30%, even more preferably at least 50%, and most preferably at least 75% of the fungi contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors.
  • According to one embodiment of the use and the method for combating phytopathogenic fungi, wherein the mutation in the mitochondrial cytochrome b gene of the phytopathogenic fungi is G143A.
  • According to another embodiment, the phytopathogenic fungi are selected from the group consisting of basidomycetes, ascomycetes, and oomycetes.
  • According to a further embodiment, the phytopathogenic fungi are selected from the group consisting of Alternaria alternata, Blumeria graminis, Pyricularia oryzae (also known as Magnaporthe grisea), Septoria tritici (also known as Mycosphaerella graminicola), Mycosphaerella fijiensis, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis and Plasmopara viticola, in particular Septoria tritici.
  • One embodiment of the invention relates to compounds I, wherein R1 is halogen, C1-C4-alkyl, C1-C4-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl, wherein the aliphatic moieties of R1 may carry 1, 2, 3 or up to the maximum number of identical or different groups Rb which independently of one another are selected from halogen, CN, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-haloalkoxy; more preferably R1 is halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl or C1-C4-haloalkoxy-C1-C4-alkyl; even more preferably R1 is halogen, C1-C4-alkyl, C1-C4-chloroalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl or C1-C4-haloalkoxy-C1-C4-alkyl; in particular C1-C4-alkyl.
  • According to another embodiment, if R4 is 1-methoxycarbonyl-2-methoxy-ethen-1-yl (R4-2, wherein X is O), R1 cannot be CF3.
  • According to a further embodiment, R2 is hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl or C1-C4-haloalkoxy-C1-C4-alkyl; more preferably R2 is hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy, or C1-C4-alkoxy-C1-C4-alkyl; even more preferably R2 is hydrogen, C1-C4-alkyl or C1-C4-alkoxy; in particular hydrogen.
  • According to a further embodiment, R2 is halogen, C1-C4-alkyl, C1-C4-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl, wherein the aliphatic moieties of R2 may carry 1, 2, 3 or up to the maximum number of identical or different groups Ra which independently of one another are selected from halogen, CN, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-haloalkoxy.
  • According to a further embodiment, Z is hydrogen or methyl, in particular methyl.
  • According to a further embodiment, Y is a divalent group selected from —OCH2—, —CH2—, —CH2CH2—, —C(CH3)═N—O—CH2—, —O—N═C(CH3)—C(CH3)═N—O—CH2— and —C(═N—O—CH3)—C(CH3)═NO—CH2—; preferably —OCH2—, —CH2CH2—, —C(CH3)═N—O—CH2—, —O—N═C(CH3)—C(CH3)═N—O—CH2— or —C(═N—O—CH3)—C(CH3)═N—O—CH2—, where the bond depicted on the left side of the divalent group Y is attached to R3, and the bond depicted on the right side is attached to the carbon atom being substituted by R2; in particular Y is —OCH2, which compounds are of formula I.1:
  • Figure US20180360041A1-20181220-C00009
  • According to a further embodiment, Y is —CH2—, which compounds are of formula I.2:
  • Figure US20180360041A1-20181220-C00010
  • According to a further embodiment, Y is —CH2CH2—, which compounds are of formula I.3:
  • Figure US20180360041A1-20181220-C00011
  • According to a further embodiment, Y is —C(CH3)═N—O—CH2—, which compounds are of formula I.4:
  • Figure US20180360041A1-20181220-C00012
  • According to a further embodiment, Y is —O—N═C(CH3)—C(CH3)═N—O—CH2—, which compounds are of formula I.5:
  • Figure US20180360041A1-20181220-C00013
  • According to a further embodiment, Y is —C(═N—O—CH3)—C(CH3)═N—O—CH2—, which compounds are of formula I.6:
  • Figure US20180360041A1-20181220-C00014
  • Particularly preferred embodiments of the invention relate to compounds I, wherein the group Y is one of the following radicals Y-1 to Y-10, where the bond depicted on the left side of the divalent group Y is attached to R3, and the bond depicted on the right side is attached to the carbon atom being substituted by R2:
  • No. Y
    Y-1 —OCH2—
    Y-2 —CH2—
    Y-3 —CH2CH2—
    Y-4 —C(CH3)═N—O—CH2—
    Y-5 —O—N═C(CH3)—C(CH3)═N—O—CH2—
    Y-6 —C(═N—O—CH3)—C(CH3)═N—O—CH2—
    Y-7 —CH2—C(CH3)═N—O—CH2—
    Y-8 —C(═O)—C(CH3)═N—O—CH2—
    Y-9 —CH2OCH2—
    Y-10 —CH═N—O—CH2—
  • Particularly preferred embodiments of the invention relate to compounds I, wherein the group Y is —OCH2—.
  • According to a further embodiment, R3 is phenyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl wherein the ring member atoms of the heterocyclyl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, wherein R3 may carry 1, 2, 3, 4 or up to the maximum possible number of identical or different groups Rb as defined herein; more preferably said 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl is a 5- to 6-membered heteroaryl wherein the ring member atoms of the heteroaryl include besides carbon atoms 1, 2 or 3 heteroatoms selected from the group of N, O and S.
  • According to a further embodiment, R3 is phenyl, wherein the phenyl may carry 1, 2, 3, 4 or up to the maximum possible number of identical or different groups Rb as defined herein.
  • According to a further embodiment, R3 is a 5-membered-heteroaryl, wherein the ring member atoms of the heterocyclyl include besides carbon atoms 1, 2 or 3 heteroatoms selected from the group of N, O and S, wherein the heteroaryl may carry 1, 2, 3, 4 or up to the maximum possible number of identical or different groups Rb as defined herein; more preferably said heteroaryl is pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl or 1,2,4-thiadiazolyl.
  • According to a further embodiment, R3 is pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl or 1,2,4-thiadiazolyl, which is substituted by phenyl, wherein said phenyl may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rc, which may be the same or different to any other Rc, wherein Rc is halogen, C1-C4-alkyl, C2-C4-alkenyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxyimino-C1-C4-alkyl, phenyl or a 5-membered saturated, partially unsaturated or aromatic heterocyclyl which, in addition to carbon atoms, contains one to three heteroatoms from the group consisting of N, O and S as ring members; and wherein the aforementioned heterocyclyl groups Rc are attached via a direct bond, an oxygen or sulfur atom and for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rd as defined herein.
  • According to a further embodiment, R3 is a 6-membered-heteroaryl, wherein the ring member atoms of the heterocyclyl include besides carbon atoms 1, 2 or 3 heteroatoms selected from the group of N, O and S, wherein the heteroaryl may carry 1, 2, 3, 4 or up to the maximum possible number of identical or different groups Rb as defined herein; more preferably said heteroaryl is pyridinyl or pyrimidinyl.
  • According to a further embodiment, R3 carries 1, 2 or 3 identical or different groups Rb.
  • According to a further embodiment, Rb independently of one another are selected from carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyloxy, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; and wherein the aforementioned phenyl and heterocyclyl groups Rb are attached via a direct bond, an oxygen or sulfur atom.
  • According to a further embodiment, the aliphatic or cyclic groups Rb for their part carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rc, which, may be the same or different to any other Rc, selected from halogen, hydroxyl, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C8-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; more preferably Rb for their part carry 1, 2 or 3 identical or different groups Rc.
  • According to a further embodiment, Rc, which, may be the same or different to any other Rc, is halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxyimino-C1-C4-alkyl, phenyl or a 5-membered saturated, partially unsaturated or aromatic heterocyclyl which, in addition to carbon atoms, contains one to three heteroatoms from the group consisting of N, O and S as ring members; wherein the aforementioned cyclic groups Rc are attached via a direct bond, an oxygen or sulfur atom and for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rd as defined herein.
  • According to a further embodiment, two radicals Rb that are bound to adjacent ring member atoms of the cyclic group R3 form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic cycle, which may be a carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S.
  • According to a further embodiment, R3 is —CRA═N—O—RB, wherein RA is amino, hydroxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C2-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C4-alkoxyimino-C1-C4-alkyl, C1-C4-alkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyloxy, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; and wherein the aforementioned phenyl and heterocyclyl groups RA are attached via a direct bond, an oxygen or sulfur atom, where the aliphatic or cyclic groups RA may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Re, which may be the same or different to any other Re, is halogen, hydroxyl, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C8-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
  • According to a further embodiment, R3 is —CRA═N—O—RB, wherein RB is hydroxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C1-C4-alkoxyimino-C1-C4-alkylC1-C4-alkoxycarbonyl, phenyl, naphthyl or a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members, where the aliphatic or cyclic groups RB may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Re, which may be the same or different to any other Re, is halogen, hydroxyl, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C8-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
  • More preferably RA and RB, independently of each other, are C1-C4-alkyl which may carry 1, 2, 3 or up to the maximum possible number of identical or different halogen; in particular RA and RB are methyl.
  • According to a further embodiment, the aliphatic or cyclic groups RA and/or RB for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Re, more preferably they carry 0, 1 or 3 identical or different groups Re.
  • According to a further embodiment, Re, which may be the same or different to any other Re, is halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
  • According to a further embodiment, R4 is —C(═NOCH3)—CONHCH3, —C(═NOCH3)—COOCH3, —C(═CHOCH3)—COOCH3, —C(═CHOCH3)—CONHCH3, —N(OCH3)—COOCH3, —N(CH3)—COOCH3 or —N(CH2CH3)—COOCH3
  • According to a further embodiment, R4 is R4-1 as defined herein, wherein X is O.
  • According to a further embodiment, R4 is R4-1 as defined herein, wherein X is NH.
  • According to a further embodiment, R4 is R4-2 as defined herein, wherein X is O.
  • According to a further embodiment, R4 is R4-2 as defined herein, wherein X is NH.
  • According to a further embodiment, R4 is R4-3 as defined herein, wherein X is O.
  • According to a further embodiment, R4 is R4-3 as defined herein, wherein X is NH.
  • According to a further embodiment, R4 is R4-4 as defined herein, wherein X is O.
  • According to a further embodiment, R4 is R4-4 as defined herein, wherein X is NH.
  • According to a further embodiment, R5 is C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy, more preferably C1-C2-alkyl or C1-C2-alkoxy, even more preferably methyl, ethyl or methoxy.
  • According to a further embodiment, R4 is R4-4 as defined herein, wherein X is O and wherein R5 is methyl, ethyl or methoxy.
  • According to a further embodiment, R4 is R4-5 as defined herein, wherein X is O.
  • According to a further embodiment, R4 is R4-5 as defined herein, wherein X is NH.
  • According to a further embodiment, R4 is R4-6 as defined herein.
  • According to a further embodiment, R4 is R4-7 as defined herein.
  • Further embodiments of the invention relate to compounds I, wherein the group R3 is one of the following radicals R3-A to R3-B, wherein # indicates the point of attachment to the linker moiety Y:
  • Line R3
    R3-A
    Figure US20180360041A1-20181220-C00015
    R3-B
    Figure US20180360041A1-20181220-C00016
  • Particularly preferred embodiments of the invention relate to compounds I, wherein the group R3 is one of the following radicals R3-1 to R3-195, wherein # indicates the point of attachment to the linker moiety Y:
  • TABLE A
    Line R3
    R3-1
    Figure US20180360041A1-20181220-C00017
    R3-2
    Figure US20180360041A1-20181220-C00018
    R3-3
    Figure US20180360041A1-20181220-C00019
    R3-4
    Figure US20180360041A1-20181220-C00020
    R3-5
    Figure US20180360041A1-20181220-C00021
    R3-6
    Figure US20180360041A1-20181220-C00022
    R3-7
    Figure US20180360041A1-20181220-C00023
    R3-8
    Figure US20180360041A1-20181220-C00024
    R3-9
    Figure US20180360041A1-20181220-C00025
    R3-10
    Figure US20180360041A1-20181220-C00026
    R3-11
    Figure US20180360041A1-20181220-C00027
    R3-12
    Figure US20180360041A1-20181220-C00028
    R3-13
    Figure US20180360041A1-20181220-C00029
    R3-14
    Figure US20180360041A1-20181220-C00030
    R3-15
    Figure US20180360041A1-20181220-C00031
    R3-16
    Figure US20180360041A1-20181220-C00032
    R3-17
    Figure US20180360041A1-20181220-C00033
    R3-18
    Figure US20180360041A1-20181220-C00034
    R3-19
    Figure US20180360041A1-20181220-C00035
    R3-20
    Figure US20180360041A1-20181220-C00036
    R3-21
    Figure US20180360041A1-20181220-C00037
    R3-22
    Figure US20180360041A1-20181220-C00038
    R3-23
    Figure US20180360041A1-20181220-C00039
    R3-24
    Figure US20180360041A1-20181220-C00040
    R3-25
    Figure US20180360041A1-20181220-C00041
    R3-26
    Figure US20180360041A1-20181220-C00042
    R3-27
    Figure US20180360041A1-20181220-C00043
    R3-28
    Figure US20180360041A1-20181220-C00044
    R3-29
    Figure US20180360041A1-20181220-C00045
    R3-30
    Figure US20180360041A1-20181220-C00046
    R3-31
    Figure US20180360041A1-20181220-C00047
    R3-32
    Figure US20180360041A1-20181220-C00048
    R3-33
    Figure US20180360041A1-20181220-C00049
    R3-34
    Figure US20180360041A1-20181220-C00050
    R3-35
    Figure US20180360041A1-20181220-C00051
    R3-36
    Figure US20180360041A1-20181220-C00052
    R3-37
    Figure US20180360041A1-20181220-C00053
    R3-38
    Figure US20180360041A1-20181220-C00054
    R3-39
    Figure US20180360041A1-20181220-C00055
    R3-40
    Figure US20180360041A1-20181220-C00056
    R3-41
    Figure US20180360041A1-20181220-C00057
    R3-42
    Figure US20180360041A1-20181220-C00058
    R3-43
    Figure US20180360041A1-20181220-C00059
    R3-44
    Figure US20180360041A1-20181220-C00060
    R3-45
    Figure US20180360041A1-20181220-C00061
    R3-46
    Figure US20180360041A1-20181220-C00062
    R3-47
    Figure US20180360041A1-20181220-C00063
    R3-48
    Figure US20180360041A1-20181220-C00064
    R3-49
    Figure US20180360041A1-20181220-C00065
    R3-50
    Figure US20180360041A1-20181220-C00066
    R3-51
    Figure US20180360041A1-20181220-C00067
    R3-52
    Figure US20180360041A1-20181220-C00068
    R3-53
    Figure US20180360041A1-20181220-C00069
    R3-54
    Figure US20180360041A1-20181220-C00070
    R3-55
    Figure US20180360041A1-20181220-C00071
    R3-56
    Figure US20180360041A1-20181220-C00072
    R3-57
    Figure US20180360041A1-20181220-C00073
    R3-58
    Figure US20180360041A1-20181220-C00074
    R3-59
    Figure US20180360041A1-20181220-C00075
    R3-60
    Figure US20180360041A1-20181220-C00076
    R3-61
    Figure US20180360041A1-20181220-C00077
    R3-62
    Figure US20180360041A1-20181220-C00078
    R3-63
    Figure US20180360041A1-20181220-C00079
    R3-64
    Figure US20180360041A1-20181220-C00080
    R3-65
    Figure US20180360041A1-20181220-C00081
    R3-66
    Figure US20180360041A1-20181220-C00082
    R3-67
    Figure US20180360041A1-20181220-C00083
    R3-68
    Figure US20180360041A1-20181220-C00084
    R3-69
    Figure US20180360041A1-20181220-C00085
    R3-70
    Figure US20180360041A1-20181220-C00086
    R3-71
    Figure US20180360041A1-20181220-C00087
    R3-72
    Figure US20180360041A1-20181220-C00088
    R3-73
    Figure US20180360041A1-20181220-C00089
    R3-74
    Figure US20180360041A1-20181220-C00090
    R3-75
    Figure US20180360041A1-20181220-C00091
    R3-76
    Figure US20180360041A1-20181220-C00092
    R3-77
    Figure US20180360041A1-20181220-C00093
    R3-78
    Figure US20180360041A1-20181220-C00094
    R3-79
    Figure US20180360041A1-20181220-C00095
    R3-80
    Figure US20180360041A1-20181220-C00096
    R3-81
    Figure US20180360041A1-20181220-C00097
    R3-82
    Figure US20180360041A1-20181220-C00098
    R3-83
    Figure US20180360041A1-20181220-C00099
    R3-84
    Figure US20180360041A1-20181220-C00100
    R3-85
    Figure US20180360041A1-20181220-C00101
    R3-86
    Figure US20180360041A1-20181220-C00102
    R3-87
    Figure US20180360041A1-20181220-C00103
    R3-88
    Figure US20180360041A1-20181220-C00104
    R3-89
    Figure US20180360041A1-20181220-C00105
    R3-90
    Figure US20180360041A1-20181220-C00106
    R3-91
    Figure US20180360041A1-20181220-C00107
    R3-92
    Figure US20180360041A1-20181220-C00108
    R3-93
    Figure US20180360041A1-20181220-C00109
    R3-94
    Figure US20180360041A1-20181220-C00110
    R3-95
    Figure US20180360041A1-20181220-C00111
    R3-96
    Figure US20180360041A1-20181220-C00112
    R3-97
    Figure US20180360041A1-20181220-C00113
    R3-98
    Figure US20180360041A1-20181220-C00114
    R3-99
    Figure US20180360041A1-20181220-C00115
    R3-100
    Figure US20180360041A1-20181220-C00116
    R3-101
    Figure US20180360041A1-20181220-C00117
    R3-102
    Figure US20180360041A1-20181220-C00118
    R3-103
    Figure US20180360041A1-20181220-C00119
    R3-104
    Figure US20180360041A1-20181220-C00120
    R3-105
    Figure US20180360041A1-20181220-C00121
    R3-106
    Figure US20180360041A1-20181220-C00122
    R3-107
    Figure US20180360041A1-20181220-C00123
    R3-108
    Figure US20180360041A1-20181220-C00124
    R3-109
    Figure US20180360041A1-20181220-C00125
    R3-110
    Figure US20180360041A1-20181220-C00126
    R3-111
    Figure US20180360041A1-20181220-C00127
    R3-112
    Figure US20180360041A1-20181220-C00128
    R3-113
    Figure US20180360041A1-20181220-C00129
    R3-114
    Figure US20180360041A1-20181220-C00130
    R3-115
    Figure US20180360041A1-20181220-C00131
    R3-116
    Figure US20180360041A1-20181220-C00132
    R3-117
    Figure US20180360041A1-20181220-C00133
    R3-118
    Figure US20180360041A1-20181220-C00134
    R3-119
    Figure US20180360041A1-20181220-C00135
    R3-120
    Figure US20180360041A1-20181220-C00136
    R3-121
    Figure US20180360041A1-20181220-C00137
    R3-122
    Figure US20180360041A1-20181220-C00138
    R3-123
    Figure US20180360041A1-20181220-C00139
    R3-124
    Figure US20180360041A1-20181220-C00140
    R3-125
    Figure US20180360041A1-20181220-C00141
    R3-126
    Figure US20180360041A1-20181220-C00142
    R3-127
    Figure US20180360041A1-20181220-C00143
    R3-128
    Figure US20180360041A1-20181220-C00144
    R3-129
    Figure US20180360041A1-20181220-C00145
    R3-130
    Figure US20180360041A1-20181220-C00146
    R3-131
    Figure US20180360041A1-20181220-C00147
    R3-132
    Figure US20180360041A1-20181220-C00148
    R3-133
    Figure US20180360041A1-20181220-C00149
    R3-134
    Figure US20180360041A1-20181220-C00150
    R3-135
    Figure US20180360041A1-20181220-C00151
    R3-136
    Figure US20180360041A1-20181220-C00152
    R3-137
    Figure US20180360041A1-20181220-C00153
    R3-138
    Figure US20180360041A1-20181220-C00154
    R3-139
    Figure US20180360041A1-20181220-C00155
    R3-140
    Figure US20180360041A1-20181220-C00156
    R3-141
    Figure US20180360041A1-20181220-C00157
    R3-142
    Figure US20180360041A1-20181220-C00158
    R3-143
    Figure US20180360041A1-20181220-C00159
    R3-144
    Figure US20180360041A1-20181220-C00160
    R3-145
    Figure US20180360041A1-20181220-C00161
    R3-146
    Figure US20180360041A1-20181220-C00162
    R3-147
    Figure US20180360041A1-20181220-C00163
    R3-148
    Figure US20180360041A1-20181220-C00164
    R3-149
    Figure US20180360041A1-20181220-C00165
    R3-150
    Figure US20180360041A1-20181220-C00166
    R3-151
    Figure US20180360041A1-20181220-C00167
    R3-152
    Figure US20180360041A1-20181220-C00168
    R3-153
    Figure US20180360041A1-20181220-C00169
    R3-154
    Figure US20180360041A1-20181220-C00170
    R3-155
    Figure US20180360041A1-20181220-C00171
    R3-156
    Figure US20180360041A1-20181220-C00172
    R3-157
    Figure US20180360041A1-20181220-C00173
    R3-158
    Figure US20180360041A1-20181220-C00174
    R3-159
    Figure US20180360041A1-20181220-C00175
    R3-160
    Figure US20180360041A1-20181220-C00176
    R3-161
    Figure US20180360041A1-20181220-C00177
    R3-162
    Figure US20180360041A1-20181220-C00178
    R3-163
    Figure US20180360041A1-20181220-C00179
    R3-164
    Figure US20180360041A1-20181220-C00180
    R3-165
    Figure US20180360041A1-20181220-C00181
    R3-166
    Figure US20180360041A1-20181220-C00182
    R3-167
    Figure US20180360041A1-20181220-C00183
    R3-168
    Figure US20180360041A1-20181220-C00184
    R3-169
    Figure US20180360041A1-20181220-C00185
    R3-170
    Figure US20180360041A1-20181220-C00186
    R3-171
    Figure US20180360041A1-20181220-C00187
    R3-172
    Figure US20180360041A1-20181220-C00188
    R3-173
    Figure US20180360041A1-20181220-C00189
    R3-174
    Figure US20180360041A1-20181220-C00190
    R3-175
    Figure US20180360041A1-20181220-C00191
    R3-176
    Figure US20180360041A1-20181220-C00192
    R3-177
    Figure US20180360041A1-20181220-C00193
    R3-178
    Figure US20180360041A1-20181220-C00194
    R3-179
    Figure US20180360041A1-20181220-C00195
    R3-180
    Figure US20180360041A1-20181220-C00196
    R3-181
    Figure US20180360041A1-20181220-C00197
    R3-182
    Figure US20180360041A1-20181220-C00198
    R3-183
    Figure US20180360041A1-20181220-C00199
    R3-184
    Figure US20180360041A1-20181220-C00200
    R3-185
    Figure US20180360041A1-20181220-C00201
    R3-186
    Figure US20180360041A1-20181220-C00202
    R3-187
    Figure US20180360041A1-20181220-C00203
    R3-188
    Figure US20180360041A1-20181220-C00204
    R3-189
    Figure US20180360041A1-20181220-C00205
    R3-190
    Figure US20180360041A1-20181220-C00206
    R3-191
    Figure US20180360041A1-20181220-C00207
    R3-192
    Figure US20180360041A1-20181220-C00208
    R3-193
    Figure US20180360041A1-20181220-C00209
    R3-194
    Figure US20180360041A1-20181220-C00210
    R3-195
    Figure US20180360041A1-20181220-C00211

    wherein # indicates the point of attachment to the linker moiety Y.
  • Preferred embodiments of the invention relate to compounds I, wherein the group R3 is R3-A, in particular R3-1 (1-(4-chlorophenyl)-pyrazol-3-yl).
  • The compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • The compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
  • Preferably, compounds I and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • The term “plant propagation material” is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • Preferably, treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • The term “cultivated plants” is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. cf. http://cera-gmc.org/, see GM crop database therein). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted posttranslational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
  • Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici(anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e.g. B. oryzae on rice and turfs; Blumeria (formerly Elysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e.g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria 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 chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani on soybeans and F. verticillioides 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 bewellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad-leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or ‘rotbrenner’, anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. 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. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici(Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum and 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 and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
  • The compounds I and compositions thereof, respectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
  • The term “plant health” is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves (“greening effect”)), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
  • The compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
  • The compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
  • The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
  • An agrochemical composition comprises a fungicidally effective amount of a compound I. The term “effective amount” denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
  • The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
  • The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • Examples for composition types and their preparation are:
    • i) Water-Soluble Concentrates (SL, LS)
  • 10-60 wt % of a compound I and 5-15 wt % wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) ad 100 wt %. The active substance dissolves upon dilution with water.
    • ii) Dispersible Concentrates (DC)
  • 5-25 wt % of a compound I and 1-10 wt % dispersant (e. g. polyvinylpyrrolidone) are dissolved in organic solvent (e.g. cyclohexanone) ad 100 wt %. Dilution with water gives a dispersion.
  • iii) Emulsifiable Concentrates (EC)
  • 15-70 wt % of a compound I and 5-10 wt % emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e.g. aromatic hydrocarbon) ad 100 wt %. Dilution with water gives an emulsion.
    • iv) Emulsions (EW, EO, ES)
  • 5-40 wt % of a compound I and 1-10 wt % emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt % water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt % by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
    • v) Suspensions (SC, OD, FS)
  • In an agitated ball mill, 20-60 wt % of a compound I are comminuted with addition of 2-10 wt % dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt % thickener (e.g. xanthan gum) and water ad 100 wt % to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt % binder (e.g. polyvinylalcohol) is added.
    • vi) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)
  • 50-80 wt % of a compound I are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt % and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • vii) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, WS)
  • 50-80 wt % of a compound I are ground in a rotor-stator mill with addition of 1-5 wt % dispersants (e.g. sodium lignosulfonate), 1-3 wt % wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt %. Dilution with water gives a stable dispersion or solution of the active substance.
  • viii) Gel (GW, GF)
  • In an agitated ball mill, 5-25 wt % of a compound I are comminuted with addition of 3-10 wt % dispersants (e.g. sodium lignosulfonate), 1-5 wt % thickener (e.g. carboxymethylcellulose) and water ad 100 wt % to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
    • iv) Microemulsion (ME)
  • 5-20 wt % of a compound I are added to 5-30 wt % organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt % surfactant blend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100%. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
    • iv) Microcapsules (CS)
  • An oil phase comprising 5-50 wt % of a compound I, 0-40 wt % water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt % acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt % of a compound I according to the invention, 0-40 wt % water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4′-diisocyanate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1-10 wt %. The wt % relate to the total CS composition.
    • ix) Dustable Powders (DP, DS)
  • 1-10 wt % of a compound I are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt %.
    • x) Granules (GR, FG)
  • 0.5-30 wt % of a compound I is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt %. Granulation is achieved by extrusion, spray-drying or fluidized bed.
    • xi) Ultra-Low Volume Liquids (UL)
  • 1-50 wt % of a compound I are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt %.
  • The compositions types i) to xi) may optionally comprise further auxiliaries, such as 0.1-1 wt % bactericides, 5-15 wt % anti-freezing agents, 0.1-1 wt % anti-foaming agents, and 0.1-1 wt % colorants.
  • The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying compound I and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
  • In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
  • When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
  • The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained.
  • The following list of active substances, in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:
    • A) Respiration inhibitors
      • Inhibitors of complex III at Qo site (e.g. strobilurins): azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone;
      • inhibitors of complex III at Qi site: cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate; (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl 2-methylpropanoate
      • inhibitors of complex II (e. g. carboxamides): benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4′-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1,3-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1,3,5-trimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide;
      • other respiration inhibitors (e.g. complex I, uncouplers): diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthiofam;
    • B) Sterol biosynthesis inhibitors (SBI fungicides)
      • C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1H-[1,2,4]triazole, 2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiranylmethyl]-2H-[1,2,4]triazole-3-thiol; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine;
      • Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
      • Inhibitors of 3-keto reductase: fenhexamid;
    • C) Nucleic acid synthesis inhibitors
      • phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
      • others: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;
    • D) Inhibitors of cell division and cytoskeleton
      • tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine
      • other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
    • E) Inhibitors of amino acid and protein synthesis
      • methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil, mepanipyrim, pyrimethanil;
      • protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
    • F) Signal transduction inhibitors
      • MAP/histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;
      • G protein inhibitors: quinoxyfen;
    • G) Lipid and membrane synthesis inhibitors
      • Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane;
      • lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
      • phospholipid biosynthesis and cell wall deposition: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
      • compounds affecting cell membrane permeability and fatty acids: propamocarb, propamocarb-hydrochlorid
      • fatty acid amide hydrolase inhibitors: 1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone
    • H) Inhibitors with Multi Site Action
      • inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
      • thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;
      • organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
      • guanidines and others: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetraone;
    • I) Cell wall synthesis inhibitors
      • inhibitors of glucan synthesis: validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
    • J) Plant defence inducers
      • acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
    • K) Unknown mode of action
      • bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxathiapiprolin, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoromethoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N′-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N′-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N′-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N′-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanylpropoxy)-phenyl)-N-ethyl-N-methyl formamidine, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole),
      • N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole, 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
    • L) Antifungal biocontrol agents, plant bioactivators: Ampelomyces quisqualis (e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany), Aspergillus flavus (e.g. AFLAGUARD® from Syngenta, CH), Aureobasidium pullulans (e.g. BOTECTOR® from bio-ferm GmbH, Germany), Bacillus pumilus (e.g. NRRL Accession No. B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc., USA), Bacillus subtilis (e.g. isolate NRRL-Nr. B-21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest Inc., USA), Bacillus subtilis var. amyloliquefaciens FZB24 (e.g. TAEGRO® from Novozyme Biologicals, Inc., USA), Candida oleophila I-82 (e.g. ASPIRE® from Ecogen Inc., USA), Candida saitoana (e.g. BIOCURE® (in mixture with lysozyme) and BIOCOAT® from Micro Flo Company, USA (BASF SE) and Arysta), Chitosan (e.g. ARMOUR-ZEN from BotriZen Ltd., NZ), Clonostachys rosea f. catenulata, also named Gliocladium catenulatum (e.g. isolate J1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS® from Prophyta, Germany), Cryphonectria parasitica (e.g. Endothia parasitica from CNICM, France), Cryptococcus albidus (e.g. YIELD PLUS® from Anchor Bio-Technologies, South Africa), Fusarium oxysporum (e.g. BIOFOX® from S.I.A.P.A., Italy, FUSACLEAN® from Natural Plant Protection, France), Metschnikowia fructicola (e.g. SHEMER® from Agrogreen, Israel), Microdochium dimerum (e.g. ANTIBOT® from Agrauxine, France), Phlebiopsis gigantea (e.g. ROTSOP® from Verdera, Finland), Pseudozyma flocculosa (e.g. SPORODEX® from Plant Products Co. Ltd., Canada), Pythium oligandrum DV74 (e.g. POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria sachlinensis (e.g. REGALIA® from Marrone BioInnovations, USA), Talaromyces flavus V117b (e.g. PROTUS® from Prophyta, Germany), Trichoderma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan), T. atroviride LC52 (e.g. SENTINEL® from Agrimm Technologies Ltd, NZ), T. harzianumT-22 (e.g. PLANTSHIELD® der Firma BioWorks Inc., USA), T. harzianum TH 35 (e.g. ROOT PRO® from Mycontrol Ltd., Israel), T. harzianum T-39 (e.g. TRICHODEX® and TRICHODERMA 2000® from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride (e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum ICC012 and T. viride ICC080 (e.g. REMEDIER® WP from Isagro Ricerca, Italy), T. polysporum and T. harzianum (e.g. BINAB® from BINAB Bio-Innovation AB, Sweden), T. stromaticum (e.g. TRICOVAB® from C.E.P.L.A.C., Brazil), T. virens GL-21 (e.g. SOILGARD® from Certis LLC, USA), T. viride (e.g. TRIECO® from Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE® F from T. Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride TV1 from Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (e.g. BOTRY-ZEN® from Botry-Zen Ltd, NZ);
    • M) Growth regulators
      abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid, trinexapac-ethyl and uniconazole;
    • N) Herbicides
      • acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
      • amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
      • aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
      • Bipyridyls: diquat, paraquat;
      • (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;
      • cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim;
      • dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin;
      • diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen;
      • hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;
      • imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;
      • phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
      • pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
      • pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;
      • sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea;
      • triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
      • ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, methabenzthiazuron, tebuthiuron;
      • other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
      • others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester.
    • O) Insecticides
      • organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
      • carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;
      • pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin;
      • insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
      • nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, flupyradifurone, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-2-chloro-thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1,3,5]triazinane;
      • GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1-(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1H-pyrazole-3-carbothioic acid amide;
      • macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram;
      • mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
      • METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon;
      • Uncouplers: chlorfenapyr;
      • oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite;
      • moulting disruptor compounds: cryomazine;
      • mixed function oxidase inhibitors: piperonyl butoxide;
      • sodium channel blockers: indoxacarb, metaflumizone;
      • others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, and pyrifluquinazon.
  • The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to L), as described above, and if desired one suitable solvent or solid carrier. Those mixtures are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi. Furthermore, combating harmful fungi with a mixture of compounds I and at least one fungicide from groups A) to L), as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups A) to L). By applying compounds I together with at least one active substance from groups A) to O) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic mixtures). This can be obtained by applying the compounds I and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or separately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.
  • In binary mixtures, i.e. compositions according to the invention comprising one compound I (component 1) and one further active substance (component 2), e. g. one active substance from groups A) to O), the weight ratio of component 1 and component 2 generally depends from the properties of the active substances used, usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1:3 to 3:1.
  • In ternary mixtures, i.e. compositions according to the invention comprising one compound I (component 1) and a first further active substance (component 2) and a second further active substance (component 3), e. g. two active substances from groups A) to O), the weight ratio of component 1 and component 2 depends from the properties of the active substances used, preferably it is in the range of from 1:50 to 50:1 and particularly in the range of from 1:10 to 10:1, and the weight ratio of component 1 and component 3 preferably is in the range of from 1:50 to 50:1 and particularly in the range of from 1:10 to 10:1.
  • Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group A) (component 2) and particularly selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin; famoxadone, fenamidone; benzovindiflupyr, bixafen, boscalid, fluopyram, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, sedaxane; ametoctradin, cyazofamid, fluazinam, fentin salts, such as fentin acetate.
  • Preference is given to mixtures comprising a compound of formula I (component 1) and at least one active substance selected from group B) (component 2) and particularly selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, fenarimol, triforine; dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine; fenhexamid.
  • Preference is given to mixtures comprising a compound of formula I (component 1) and at least one active substance selected from group C) (component 2) and particularly selected from metalaxyl, (metalaxyl-M) mefenoxam, ofurace.
  • Preference is given to mixtures comprising a compound of formula I (component 1) and at least one active substance selected from group D) (component 2) and particularly selected from benomyl, carbendazim, thiophanate-methyl, ethaboxam, fluopicolide, zoxamide, metrafenone, pyriofenone.
  • Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group E) (component 2) and particularly selected from cyprodinil, mepanipyrim, pyrimethanil.
  • Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group F) (component 2) and particularly selected from iprodione, fludioxonil, vinclozolin, quinoxyfen.
  • Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group G) (component 2) and particularly selected from dimethomorph, flumorph, iprovalicarb, benthiavalicarb, mandipropamid, propamocarb.
  • Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group H) (component 2) and particularly selected from copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, mancozeb, metiram, propineb, thiram, captafol, folpet, chlorothalonil, dichlofluanid, dithianon.
  • Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group I) (component 2) and particularly selected from carpropamid and fenoxanil.
  • Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group J) (component 2) and particularly selected from acibenzolar-S-methyl, probenazole, tiadinil, fosetyl, fosetyl-aluminium, H3PO3 and salts thereof.
  • Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group K) (component 2) and particularly selected from cymoxanil, proquinazid and N-methyl-2-{1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide.
  • Preference is also given to mixtures comprising a compound 1 (component 1) and at least one active substance selected from group L) (component 2) and particularly selected from Bacillus subtilis strain NRRL No. B-21661, Bacillus pumilus strain NRRL No. B-30087 and Ulocladium oudemansii.
  • Accordingly, the present invention furthermore relates to compositions comprising one compound I (component 1) and one further active substance (component 2), which further active substance is selected from the column “Component 2” of the lines B-1 to B-369 of Table B.
  • A further embodiment relates to the compositions B-1 to B-369 listed in Table B, where a row of Table B corresponds in each case to a fungicidal composition comprising one of the in the present specification individualized compounds of formula I (component 1) and the respective further active substance from groups A) to O) (component 2) stated in the row in question. Preferably, the compositions described comprise the active substances in synergistically effective amounts.
  • TABLE B
    Composition comprising one indiviualized compound I
    and one further active substance from groups A) to O)
    Mixture Component 1 Component 2
    B-1 one individualized compound I Azoxystrobin
    B-2 one individualized compound I Coumethoxystrobin
    B-3 one individualized compound I Coumoxystrobin
    B-4 one individualized compound I Dimoxystrobin
    B-5 one individualized compound I Enestroburin
    B-6 one individualized compound I Fenaminstrobin
    B-7 one individualized compound I Fenoxystrobin/Flufenoxystrobin
    B-8 one individualized compound I Fluoxastrobin
    B-9 one individualized compound I Kresoxim-methyl
    B-10 one individualized compound I Metominostrobin
    B-11 one individualized compound I Orysastrobin
    B-12 one individualized compound I Picoxystrobin
    B-13 one individualized compound I Pyraclostrobin
    B-14 one individualized compound I Pyrametostrobin
    B-15 one individualized compound I Pyraoxystrobin
    B-16 one individualized compound I Pyribencarb
    B-17 one individualized compound I Trifloxystrobin
    B-18 one individualized compound I Triclopyricarb/Chlorodincarb
    B-19 one individualized compound I 2-[2-(2,5-dimethyl-phenoxy-methyl)-
    phenyl]-3-methoxy-acrylic acid methyl
    ester
    B-20 one individualized compound I 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-
    allylideneaminooxymethyl)-phenyl)-
    2-methoxyimino-N-methyl-acetamide
    B-21 one individualized compound I Benalaxyl
    B-22 one individualized compound I Benalaxyl-M
    B-23 one individualized compound I Benodanil
    B-24 one individualized compound I Benzovindiflupyr
    B-25 one individualized compound I Bixafen
    B-26 one individualized compound I Boscalid
    B-27 one individualized compound I Carboxin
    B-28 one individualized compound I Fenfuram
    B-29 one individualized compound I Fenhexamid
    B-30 one individualized compound I Flutolanil
    B-31 one individualized compound I Fluxapyroxad
    B-32 one individualized compound I Furametpyr
    B-33 one individualized compound I Isopyrazam
    B-34 one individualized compound I Isotianil
    B-35 one individualized compound I Kiralaxyl
    B-36 one individualized compound I Mepronil
    B-37 one individualized compound I Metalaxyl
    B-38 one individualized compound I Metalaxyl-M
    B-39 one individualized compound I Ofurace
    B-40 one individualized compound I Oxadixyl
    B-41 one individualized compound I Oxycarboxin
    B-42 one individualized compound I Penflufen
    B-43 one individualized compound I Penthiopyrad
    B-44 one individualized compound I Sedaxane
    B-45 one individualized compound I Tecloftalam
    B-46 one individualized compound I Thifluzamide
    B-47 one individualized compound I Tiadinil
    B-48 one individualized compound I 2-Amino-4-methyl-thiazole-5-carboxylic
    acid anilide
    B-49 one individualized compound I N-(4′-trifluoromethylthiobiphenyl-2-yl)-
    3-difluoromethyl-1-methyl-1H-pyrazole-
    4-carboxamide
    B-50 one individualized compound I N-(2-(1,3,3-trimethyl-butyl)-phenyl)-
    1,3-dimethyl-5-fluoro-1H-pyrazole-
    4-carboxamide
    B-51 one individualized compound I 3-(difluoromethyl)-1-methyl-N-(1,1,3-tri-
    methylindan-4-yl)pyrazole-4-carboxamide
    B-52 one individualized compound I 3-(trifluoromethyl)-1-methyl-N-(1,1,3-tri-
    methylindan-4-yl)pyrazole-4-carboxamide
    B-53 one individualized compound I 1,3-dimethyl-N-(1,1,3-trimethylindan-
    4-yl)pyrazole-4-carboxamide
    B-54 one individualized compound I 3-(trifluoromethyl)-1,5-dimethyl-
    N-(1,1,3-trimethylindan-4-yl)pyrazole-
    4-carboxamide
    B-55 one individualized compound I 3-(difluoromethyl)-1,5-dimethyl-
    N-(1,1,3-trimethylindan-4-yl)pyrazole-
    4-carboxamide
    B-56 one individualized compound I 1,3,5-trimethyl-N-(1,1,3-trimethylindan-
    4-yl)pyrazole-4-carboxamide
    B-57 one individualized compound I Dimethomorph
    B-58 one individualized compound I Flumorph
    B-59 one individualized compound I Pyrimorph
    B-60 one individualized compound I Flumetover
    B-61 one individualized compound I Fluopicolide
    B-62 one individualized compound I Fluopyram
    B-63 one individualized compound I Zoxamide
    B-64 one individualized compound I Carpropamid
    B-65 one individualized compound I Diclocymet
    B-66 one individualized compound I Mandipropamid
    B-67 one individualized compound I Oxytetracyclin
    B-68 one individualized compound I Silthiofam
    B-69 one individualized compound I N-(6-methoxy-pyridin-3-yl) cyclopro-
    panecarboxylic acid amide
    B-70 one individualized compound I Azaconazole
    B-71 one individualized compound I Bitertanol
    B-72 one individualized compound I Bromuconazole
    B-73 one individualized compound I Cyproconazole
    B-74 one individualized compound I Difenoconazole
    B-75 one individualized compound I Diniconazole
    B-76 one individualized compound I Diniconazole-M
    B-77 one individualized compound I Epoxiconazole
    B-78 one individualized compound I Fenbuconazole
    B-79 one individualized compound I Fluquinconazole
    B-80 one individualized compound I Flusilazole
    B-81 one individualized compound I Flutriafol
    B-82 one individualized compound I Hexaconazol
    B-83 one individualized compound I Imibenconazole
    B-84 one individualized compound I Ipconazole
    B-85 one individualized compound I Metconazole
    B-86 one individualized compound I Myclobutanil
    B-87 one individualized compound I Oxpoconazol
    B-88 one individualized compound I Paclobutrazol
    B-89 one individualized compound I Penconazole
    B-90 one individualized compound I Propiconazole
    B-91 one individualized compound I Prothioconazole
    B-92 one individualized compound I Simeconazole
    B-93 one individualized compound I Tebuconazole
    B-94 one individualized compound I Tetraconazole
    B-95 one individualized compound I Triadimefon
    B-96 one individualized compound I Triadimenol
    B-97 one individualized compound I Triticonazole
    B-98 one individualized compound I Uniconazole
    B-99 one individualized compound I 1-[rel-A(2S;3R)-3-(2-chlorophenyl)-
    2-(2,4-difluorophenyl)-oxiranylmethyl]-
    5-thiocyanato-1H-[1,2,4]triazole,
    B-100 one individualized compound I 2-[rel-(2S;3R)-3-(2-chlorophenyl)-
    2-(2,4-difluorophenyl)-oxiranylmethyl]-
    2H-[1,2,4]triazole-3-thiol
    B-101 one individualized compound I Cyazofamid
    B-102 one individualized compound I Amisulbrom
    B-103 one individualized compound I Imazalil
    B-104 one individualized compound I Imazalil-sulfate
    B-105 one individualized compound I Pefurazoate
    B-106 one individualized compound I Prochloraz
    B-107 one individualized compound I Triflumizole
    B-108 one individualized compound I Benomyl
    B-109 one individualized compound I Carbendazim
    B-110 one individualized compound I Fuberidazole
    B-111 one individualized compound I Thiabendazole
    B-112 one individualized compound I Ethaboxam
    B-113 one individualized compound I Etridiazole
    B-114 one individualized compound I Hymexazole
    B-115 one individualized compound I 2-(4-Chloro-phenyl)-N-[4-(3,4-dimethoxy-
    phenyl)-isoxazol-5-yl]-2-prop-2-yn-
    yloxy-acetamide
    B-116 one individualized compound I Fluazinam
    B-117 one individualized compound I Pyrifenox
    B-118 one individualized compound I 3-[5-(4-Chloro-phenyl)-2,3-dimethyl-is-
    oxazolidin-3-yl]-pyridine (Pyrisoxazole)
    B-119 one individualized compound I 3-[5-(4-Methyl-phenyl)-2,3-dimethyl-
    isoxazolidin-3-yl]-pyridine
    B-120 one individualized compound I Bupirimate
    B-121 one individualized compound I Cyprodinil
    B-122 one individualized compound I 5-Fluorocytosine
    B-123 one individualized compound I 5-Fluoro-2-(p-tolylmethoxy)pyrimidin-
    4-amine
    B-124 one individualized compound I 5-Fluoro-2-(4-fluorophenylmethoxy)py-
    rimidin-4-amine
    B-125 one individualized compound I Diflumetorim
    B-126 one individualized compound I (5,8-Difluoroquinazolin-4-yl)-{2-[2-fluoro-
    4-(4-trifluoromethyl-pyridin-2-yloxy)-
    phenyl]-ethyl}-amine
    B-127 one individualized compound I Fenarimol
    B-128 one individualized compound I Ferimzone
    B-129 one individualized compound I Mepanipyrim
    B-130 one individualized compound I Nitrapyrin
    B-131 one individualized compound I Nuarimol
    B-132 one individualized compound I Pyrimethanil
    B-133 one individualized compound I Triforine
    B-134 one individualized compound I Fenpiclonil
    B-135 one individualized compound I Fludioxonil
    B-136 one individualized compound I Aldimorph
    B-137 one individualized compound I Dodemorph
    B-138 one individualized compound I Dodemorph-acetate
    B-139 one individualized compound I Fenpropimorph
    B-140 one individualized compound I Tridemorph
    B-141 one individualized compound I Fenpropidin
    B-142 one individualized compound I Fluoroimid
    B-143 one individualized compound I Iprodione
    B-144 one individualized compound I Procymidone
    B-145 one individualized compound I Vinclozolin
    B-146 one individualized compound I Famoxadone
    B-147 one individualized compound I Fenamidone
    B-148 one individualized compound I Flutianil
    B-149 one individualized compound I Octhilinone
    B-150 one individualized compound I Probenazole
    B-151 one individualized compound I Fenpyrazamine
    B-152 one individualized compound I Acibenzolar-S-methyl
    B-153 one individualized compound I Ametoctradin
    B-154 one individualized compound I Amisulbrom
    B-155 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[(3-iso-
    butyryloxymethoxy-4-methoxypyridine-2-
    carbonyl)amino]-6-methyl-4,9-dioxo-
    [1,5]dioxonan-7-yl] 2-methylpropanoate
    B-156 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-
    4-methoxy-pyridine-2-carbonyl)amino]-
    6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]
    2-methylpropanoate
    B-157 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[[3-
    (acetoxymethoxy)-4-methoxy-pyridine-2-
    carbonyl]amino]-6-methyl-4,9-dioxo-1,5-
    dioxonan-7-yl] 2-methylpropanoate
    B-158 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[(3-iso-
    butoxycarbonyloxy-4-methoxy-pyridine-
    2-carbonyl)amino]-6-methyl-4,9-dioxo-
    1,5-dioxonan-7-yl] 2-methylpropanoate
    B-159 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-
    benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-
    2-carbonyl]amino]-6-methyl-4,9-dioxo-
    1,5-dioxonan-7-yl] 2-methylpropanoate
    B-160 one individualized compound I (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-
    2-pyridinyl)carbonyl]amino]-6-methyl-
    4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl
    2-methylpropanoate
    B-161 one individualized compound I Anilazin
    B-162 one individualized compound I Blasticidin-S
    B-163 one individualized compound I Captafol
    B-164 one individualized compound I Captan
    B-165 one individualized compound I Chinomethionat
    B-166 one individualized compound I Dazomet
    B-167 one individualized compound I Debacarb
    B-168 one individualized compound I Diclomezine
    B-169 one individualized compound I Difenzoquat,
    B-170 one individualized compound I Difenzoquat-methylsulfate
    B-171 one individualized compound I Fenoxanil
    B-172 one individualized compound I Folpet
    B-173 one individualized compound I Oxolinsäure
    B-174 one individualized compound I Piperalin
    B-175 one individualized compound I Proquinazid
    B-176 one individualized compound I Pyroquilon
    B-177 one individualized compound I Quinoxyfen
    B-178 one individualized compound I Triazoxid
    B-179 one individualized compound I Tricyclazole
    B-180 one individualized compound I 2-Butoxy-6-iodo-3-propyl-chromen-4-one
    B-181 one individualized compound I 5-Chloro-1-(4,6-dimethoxy-pyrimidin-2-
    yl)-2-methyl-1H-benzoimidazole
    B-182 one individualized compound I 5-Chloro-7-(4-methyl-piperidin-1-yl)-
    6-(2,4,6-trifluoro-phenyl)-[1,2,4]tria-
    zolo[1,5-a]pyrimidine
    B-183 one individualized compound I Ferbam
    B-184 one individualized compound I Mancozeb
    B-185 one individualized compound I Maneb
    B-186 one individualized compound I Metam
    B-187 one individualized compound I Methasulphocarb
    B-188 one individualized compound I Metiram
    B-189 one individualized compound I Propineb
    B-190 one individualized compound I Thiram
    B-191 one individualized compound I Zineb
    B-192 one individualized compound I Ziram
    B-193 one individualized compound I Diethofencarb
    B-194 one individualized compound I Benthiavalicarb
    B-195 one individualized compound I Iprovalicarb
    B-196 one individualized compound I Propamocarb
    B-197 one individualized compound I Propamocarb hydrochlorid
    B-198 one individualized compound I Valifenalate
    B-199 one individualized compound I N-(1-(1-(4-cyanophenyl)ethanesulfon-
    yl)-but-2-yl) carbamic acid-(4-fluorophenyl)
    ester
    B-200 one individualized compound I Dodine
    B-201 one individualized compound I Dodine free base
    B-202 one individualized compound I Guazatine
    B-203 one individualized compound I Guazatine-acetate
    B-204 one individualized compound I Iminoctadine
    B-205 one individualized compound I Iminoctadine-triacetate
    B-206 one individualized compound I Iminoctadine-tris(albesilate)
    B-207 one individualized compound I Kasugamycin
    B-208 one individualized compound I Kasugamycin-hydrochloride-hydrate
    B-209 one individualized compound I Polyoxine
    B-210 one individualized compound I Streptomycin
    B-211 one individualized compound I Validamycin A
    B-212 one individualized compound I Binapacryl
    B-213 one individualized compound I Dicloran
    B-214 one individualized compound I Dinobuton
    B-215 one individualized compound I Dinocap
    B-216 one individualized compound I Nitrothal-isopropyl
    B-217 one individualized compound I Tecnazen
    B-218 one individualized compound I Fentin salts
    B-219 one individualized compound I Dithianon
    B-220 one individualized compound I 2,6-dimethyl-1H,5H-[1,4]dithiino
    [2,3-c:5,6-c′]dipyrrole-
    1,3,5,7(2H,6H)-tetraone
    B-221 one individualized compound I Isoprothiolane
    B-222 one individualized compound I Edifenphos
    B-223 one individualized compound I Fosetyl, Fosetyl-aluminium
    B-224 one individualized compound I Iprobenfos
    B-225 one individualized compound I Phosphorous acid (H3PO3) and derivatives
    B-226 one individualized compound I Pyrazophos
    B-227 one individualized compound I Tolclofos-methyl
    B-228 one individualized compound I Chlorothalonil
    B-229 one individualized compound I Dichlofluanid
    B-230 one individualized compound I Dichlorophen
    B-231 one individualized compound I Flusulfamide
    B-232 one individualized compound I Hexachlorbenzene
    B-233 one individualized compound I Pencycuron
    B-234 one individualized compound I Pentachlorophenol and salts
    B-235 one individualized compound I Phthalide
    B-236 one individualized compound I Quintozene
    B-237 one individualized compound I Thiophanate Methyl
    B-238 one individualized compound I Tolylfluanid
    B-239 one individualized compound I N-(4-chloro-2-nitro-phenyl)-N-ethyl-
    4-methyl-benzenesulfonamide
    B-240 one individualized compound I Bordeaux mixture
    B-241 one individualized compound I Copper acetate
    B-242 one individualized compound I Copper hydroxide
    B-243 one individualized compound I Copper oxychloride
    B-244 one individualized compound I basic Copper sulfate
    B-245 one individualized compound I Sulfur
    B-246 one individualized compound I Biphenyl
    B-247 one individualized compound I Bronopol
    B-248 one individualized compound I Cyflufenamid
    B-249 one individualized compound I Cymoxanil
    B-250 one individualized compound I Diphenylamin
    B-251 one individualized compound I Metrafenone
    B-252 one individualized compound I Pyriofenone
    B-253 one individualized compound I Mildiomycin
    B-254 one individualized compound I Oxin-copper
    B-255 one individualized compound I Oxathiapiprolin
    B-256 one individualized compound I Prohexadione calcium
    B-257 one individualized compound I Spiroxamine
    B-258 one individualized compound I Tebufloquin
    B-259 one individualized compound I Tolylfluanid
    B-260 one individualized compound I N-(Cyclopropylmethoxyimino-(6-difluoro-
    methoxy-2,3-difluoro-phenyl)-methyl)-
    2-phenyl acetamide
    B-261 one individualized compound I N′-(4-(4-chloro-3-trifluoromethyl-
    phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-
    methyl formamidine
    B-262 one individualized compound I N′-(4-(4-fluoro-3-trifluoromethyl-
    phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-
    methyl formamidine
    B-263 one individualized compound I N′-(2-methyl-5-trifluoromethyl-4-(3-tri-
    methylsilanyl-propoxy)-phenyl)-N-ethyl-
    N-methyl formamidine
    B-264 one individualized compound I N'-(5-difluoromethyl-2-methyl-4-(3-tri-
    methylsilanyl-propoxy)-phenyl)-N-ethyl-
    N-methyl formamidine
    B-265 one individualized compound I Methoxy-acetic acid 6-tert-butyl-8-
    fluoro-2,3-dimethyl-quinolin-4-yl ester
    B-266 one individualized compound I Bacillus subtilis NRRL No. B-21661
    B-267 one individualized compound I Bacillus pumilus NRRL No. B-30087
    B-268 one individualized compound I Ulocladium oudemansii
    B-269 one individualized compound I Carbaryl
    B-270 one individualized compound I Carbofuran
    B-271 one individualized compound I Carbosulfan
    B-272 one individualized compound I Methomylthiodicarb
    B-273 one individualized compound I Bifenthrin
    B-274 one individualized compound I Cyfluthrin
    B-275 one individualized compound I Cypermethrin
    B-276 one individualized compound I alpha-Cypermethrin
    B-277 one individualized compound I zeta-Cypermethrin
    B-278 one individualized compound I Deltamethrin
    B-279 one individualized compound I Esfenvalerate
    B-280 one individualized compound I Lambda-cyhalothrin
    B-281 one individualized compound I Permethrin
    B-282 one individualized compound I Tefluthrin
    B-283 one individualized compound I Diflubenzuron
    B-284 one individualized compound I Flufenoxuron
    B-285 one individualized compound I Lufenuron
    B-286 one individualized compound I Teflubenzuron
    B-287 one individualized compound I Spirotetramate
    B-288 one individualized compound I Clothianidin
    B-289 one individualized compound I Dinotefuran
    B-290 one individualized compound I Imidacloprid
    B-291 one individualized compound I Thiamethoxam
    B-292 one individualized compound I Flupyradifurone
    B-293 one individualized compound I Acetamiprid
    B-294 one individualized compound I Thiacloprid
    B-295 one individualized compound I Endosulfan
    B-296 one individualized compound I Fipronil
    B-297 one individualized compound I Abamectin
    B-298 one individualized compound I Emamectin
    B-299 one individualized compound I Spinosad
    B-300 one individualized compound I Spinetoram
    B-301 one individualized compound I Hydramethylnon
    B-302 one individualized compound I Chlorfenapyr
    B-303 one individualized compound I Fenbutatin oxide
    B-304 one individualized compound I Indoxacarb
    B-305 one individualized compound I Metaflumizone
    B-306 one individualized compound I Flonicamid
    B-307 one individualized compound I Lubendiamide
    B-308 one individualized compound I Chlorantraniliprole
    B-309 one individualized compound I Cyazypyr (HGW86)
    B-310 one individualized compound I Cyflumetofen
    B-311 one individualized compound I Acetochlor
    B-312 one individualized compound I Dimethenamid
    B-313 one individualized compound I metolachlor
    B-314 one individualized compound I Metazachlor
    B-315 one individualized compound I Glyphosate
    B-316 one individualized compound I Glufosinate
    B-317 one individualized compound I Sulfosate
    B-318 one individualized compound I Clodinafop
    B-319 one individualized compound I Fenoxaprop
    B-320 one individualized compound I Fluazifop
    B-321 one individualized compound I Haloxyfop
    B-322 one individualized compound I Paraquat
    B-323 one individualized compound I Phenmedipham
    B-324 one individualized compound I Clethodim
    B-325 one individualized compound I Cycloxydim
    B-326 one individualized compound I Profoxydim
    B-327 one individualized compound I Sethoxydim
    B-328 one individualized compound I Tepraloxydim
    B-329 one individualized compound I Pendimethalin
    B-330 one individualized compound I Prodiamine
    B-331 one individualized compound I Trifluralin
    B-332 one individualized compound I Acifluorfen
    B-333 one individualized compound I Bromoxynil
    B-334 one individualized compound I Imazamethabenz
    B-335 one individualized compound I Imazamox
    B-336 one individualized compound I Imazapic
    B-337 one individualized compound I Imazapyr
    B-338 one individualized compound I Imazaquin
    B-339 one individualized compound I Imazethapyr
    B-340 one individualized compound I 2,4-Dichlorophenoxyacetic acid (2,4-D)
    B-341 one individualized compound I Chloridazon
    B-342 one individualized compound I Clopyralid
    B-343 one individualized compound I Fluroxypyr
    B-344 one individualized compound I Picloram
    B-345 one individualized compound I Picolinafen
    B-346 one individualized compound I Bensulfuron
    B-347 one individualized compound I Chlorimuron-ethyl
    B-348 one individualized compound I Cyclosulfamuron
    B-349 one individualized compound I Iodosulfuron
    B-350 one individualized compound I Mesosulfuron
    B-351 one individualized compound I Metsulfuron-methyl
    B-352 one individualized compound I Nicosulfuron
    B-353 one individualized compound I Rimsulfuron
    B-354 one individualized compound I Triflusulfuron
    B-355 one individualized compound I Atrazine
    B-356 one individualized compound I Hexazinone
    B-357 one individualized compound I Diuron
    B-358 one individualized compound I Florasulam
    B-359 one individualized compound I Pyroxasulfone
    B-360 one individualized compound I Bentazone
    B-361 one individualized compound I Cinidon-ethyl
    B-362 one individualized compound I Cinmethylin
    B-363 one individualized compound I Dicamba
    B-364 one individualized compound I Diflufenzopyr
    B-365 one individualized compound I Quinclorac
    B-366 one individualized compound I Quinmerac
    B-367 one individualized compound I Mesotrione
    B-368 one individualized compound I Saflufenacil
    B-369 one individualized compound I Topramezone
  • The active substances referred to as component 2, their preparation and their activity against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by IUPAC nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; U.S. Pat. No. 3,296,272; U.S. Pat. No. 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO 02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 11/028657).
  • The mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient by usual means, e. g. by the means given for the compositions of compounds I.
  • Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I.
  • The mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, it is referred to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds I, respectively.
    • I. SYNTHESIS EXAMPLES
  • With due modification of the starting compounds, the procedures shown in the synthesis examples below were used to obtain further compounds I. The resulting compounds, together with physical data, are listed in Table I below.
    • I.1 Preparation of Strobilurin Type Compounds I Example 1: Preparation of (Z)-5-[1-(4-Chloro-phenyl)-1H-pyrazol-3-yloxy]-2-[(E)-methoxyimino]-3-methyl-pent-3-enic Acid Methyl Amide (I-6)
  • Figure US20180360041A1-20181220-C00212
    • Ex. 1a: (Z)-3-Tributylstannanyl-but-2-en-1-ol (3)
  • To 156.9 ml (156.9 mmol) of a 1 molar solution of lithium-aluminum-hydride in THF 0.77 g (14.3 mmol) sodium methylate have been added and the temperature has been lowered to 0° C. afterwards. Then a solution of 10.0 g (142.7 mmol) 2-butin-1-ol in 108 ml THF has been added dropwise with stirring at this temperature. Stirring was continued for 36 h at 4° C. Thereafter, at about 0° C., 28.6 ml (292.5 mmol) ethyl acetate was-added slowly while stirring. A strongly exothermic reaction was observed. Stirring was continued for 10 min without cooling. After cooling to about 0° C., 45.8 g (142.7 mmol) tri(n-butyl)stannyl-methanolate have been added dropwise while stirring. Stirring was continued for 2 d at 4° C. After addition of 112.9 g methanol stirring was continued for 1 h at ambient temperature. The reaction mixture was poured into 250 ml of water, extracted thrice with 150 ml diethyl ether each, the combined extracts were washed twice with 80 ml of water each, then once with 40 ml saturated aqueous sodium chloride solution, dried with sodium sulfate and concentrated in vacuo. Yield 48.6 g oil, which have been purified by chromatography on 300 g silica gel with hexane/MTBE (10:1). Final yield 34.6 g (67%) oil. δ=0.90 (m); 1.30 (m); 1.50 m); 1.97 (s); 4.02 (t); 6.27 (t).
    • Ex. 1b: 1-(4-Chloro-phenyl)-3-((Z)-3-tributylstannanyl-but-2-enyloxy)-1H-pyrazole (5)
  • To 8.09 g (30.8 mmol) triphenylphosphine in 200 ml THF have been added with stirring at −75° C. 6.23 g (30.8 mmol) azodicarbonic acid diisopropyl ester. The mixture has been stirred at this temperature for 5 min. Then 10.39 g (28.8 mmol) (Z)-3-tributylstannanyl-but-2-en-1-ol have been added dropwise and stirred for 5 min at −75° C. After addition of 4.00 g (20.6 mmol) 1-(4-chlorophenyl)-3-hydroxypyrazole at −75° C. a red suspension was formed. The mixture was allowed to warm up to ambient temperature and stirred for 3 d. After removal of the solvents in vacuo 29 g oil have been collected and purified by chromatography on 120 g silica with MTBE/heptane. Yield 8.3 g (75%) oil. δ=0.85 (m); 0.95 (m); 1.30 (m); 1.50 m); 2.00 (s); 4.65 (d); 5.90 (d); 6.43 (t); 7.35 (d); 7.52 (d); 7.68 (d).
    • Ex. 1c: (Z)-5-[1-(4-Chloro-phenyl)-1H-pyrazol-3-yloxy]-2-[(E)-methoxyimino]-3-methyl-pent-3-enic Acid Methyl Ester (7)
  • 3.00 g (5.58 mmol) 1-(4-Chloro-phenyl)-3-((Z)-3-tributylstannanyl-but-2-enyloxy)-1H-pyrazole, 1.15 g (5.86 mmol) hydroxamic acid bromide (6), 0.155 g (0.67 mmol) tri(2-furyl)phosphine and 96 mg (0.17 mmol) bis(dibenzylidenacetone)-palladium have been stirred in 10 ml 1,4-dioxane for 4 d at about 80° C. After removal of the solvents in vacuo 4.3 g oil have been collected and purified by chromatography on 70 g silica with MTBE/heptane/1% triethylamine. Yield 1.2 g (59%) oil. δ=1.95 (s); 3.85 (s); 4.07 (s); 4.58 (d); 5.85 (d); 5.93 (t); 7.35 (d); 7.52 (d); 7.65 (d).
    • Ex. 1 d: (Z)-5-[1-(4-Chloro-phenyl)-1H-pyrazol-3-yloxy]-2-[(E)-methoxyimino]-3-methyl-pent-3-enic Acid Methyl Amide (I-6)
  • 120 mg (0.33 mmol) (Z)-5-[1-(4-chloro-phenyl)-1H-pyrazol-3-yloxy]-2-[(E)-methoxyimino]-3-methyl-pent-3-enic acid methyl ester and 0.99 ml (1.98 mmol) of a 2-molar solution of methyl amine in THF have been stirred overnight at ambient temperature in 2.0 ml of THF and 0.5 ml of water. After removal of the solvent in vacuo the product (120 mg) was collected in quantitative yield and good purity. Melting point 129-130° C.
    • Example 2: (Z)-5-[1-(4-Chloro-phenyl)-1H-pyrazol-3-yloxy]-2-[1-methoxy-meth-(E)-ylidene]-3-methyl-pent-3-enoic Acid Methyl Ester (Compound I-7)
  • Figure US20180360041A1-20181220-C00213
  • 1.50 g (2.79 mmol) 1-(4-Chloro-phenyl)-3-((Z)-3-tributylstannanyl-but-2-enyloxy)-1H-pyrazole (5), 0.81 g (3.35 mmol) of ester compound (8) [Chem Comm 4, 423-425, (2006)], 0.223 g (0.28 mmol) [(R)-(+)-2,2″-Bis(diphenylphosphino)-1,1″-bisnaphthyl]-palladium(II)chloride have been stirred in 14 ml 1,4-dioxane for 4.5 d at about 100° C. After removal of the solvents in vacuo the crude product has been collected, which has been purified by chromatography on 50 g silica with MTBE/hexane/2% triethylamine. Yield 0.12 g, melting point 123-125° C.
    • Example 3: Methyl N—[(Z)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-1-methyl-prop-1-enyl]-N-methyl-carbamate (I-10)
  • Figure US20180360041A1-20181220-C00214
    • Ex. 3a: 1-(4-chlorophenyl)-3-[(Z)-3-iodobut-2-enoxy]pyrazole (10)
  • To 10.0 g (18.6 mmol) 1-(4-chloro-phenyl)-3-((Z)-3-tributylstannanyl-but-2-enyloxy)-1H-pyrazole in 100 ml methylene chloride have been added 4.7 g (18.6 mmol) iodine at ambient temperature with stirring which was continued for 3 h. After removal of the solvents in vacuo the crude product was dissolved in 200 ml MTBE. 100 ml 20% aqueous potassium fluoride solution have been added and the mixture was stirred for 2 h at ambient temperature. The aqueous layer was separated and extracted with 20 ml methyltert.-butyl ether twice. The combined organic phases have been washed twice with 20 ml of water each, dried with sodium sulfate, and the solvents were removed in vacuo. The crude product (7.2 g) has been purified by chromatography on 50 g silica with methyl-tert.-butylether/hexane (1:20). Yield 5.9 g, melting point 75-77° C.
    • Ex. 3b: Methyl N—[(Z)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-1-methyl-prop-1-enyl]-N-methyl-carbamate
  • 1.50 g (4.00 mmol) 1-(4-chlorophenyl)-3-[(Z)-3-iodobut-2-enoxy]pyrazole, 0.43 g (4.81 mmol) N-methylcarbamic acid methyl ester (9), 76 mg (0.4 mmol) copperiodide, 1.27 g (6.00 mmol) potassium phosphate and 71 mg (0.80 mmol) N,N′-dimethylethylene diamine in 14 ml toluene have been stirred for 1.5 d at 100° C. After removal of the solvents in vacuo the crude product has been purified by chromatography on 50 g silica with MTBE/hexane (1:3). Yield 0.67 g. 1H-NMR (CDCl3): δ=1.90 (s); 3.05 (s); 3.70 (s); 4.68 (m); 5.63 (m); 5.90 (d); 7.35 (m); 7.55 (m); 7.68 (d).
    • Example 4: (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,4-dimethyl-pent-3-enamide (Compound I-79)
  • Figure US20180360041A1-20181220-C00215
    • Ex. 4a: 1-[1-(4-Chlorophenyl)pyrazol-3-yl]oxypropan-2-one (11)
  • 5.50 g (28.3 mmol) 1-(4-chlorophenyl)pyrazol-3-ol, 3.91 g (28.3 mmol) potassium carbonate and 50 mg sodium iodide in 30 ml DMF have been stirred for 5 min at ambient temperature. Then 2.62 g (28.3 mmol) chloroacetone have been added dropwise while stirring which was continued at 60° C. for 5 h. The mixture was poured into excess 10% aqueous lithium chloride solution and extracted with ethyl acetate three times. The combined extracts have been washed with 10% lithium chloride solution twice and dried with sodium sulfate. After removal of the solvent in vacuo the crude product has been purified by chromatography on silica. Yield 6.5 g. The product was used for the next step.
    • Ex. 4b: Methyl (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-4-methyl-pent-3-enoate and E-Isomer (13)
  • To 5.26 g (21.0 mmol) 1-[1-(4-chlorophenyl)pyrazol-3-yl]oxypropan-2-one and 7.20 g (26.9 mmol) methyl (2Z)-3-diethoxyphosphoryl-2-methoxyimino-propanoate (which can be prepared as described for the dimethoxy derivative [(Tetrahedron Let 29, 3361-3364 (1988)] in 100 ml THF have been added at ambient temperature with stirring 2.59 g (23.1 mmol) potassium tert.-butylate. Stirring was continued over night. After removal of the solvent in vacuo the mixture was purified by chromatography on silica with heptane/ethyl acetate. 1.07 g of a 80:20 E:Z-mixture have been collected. This has been used directly for the next step.
    • Ex. 4c: Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,4-dimethyl-pent-3-enamide
  • 0.68 g (1.87 mmol) methyl (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-4-methyl-pent-3-enoate and E-isomer from the previous reaction have been dissolved in 3.0 ml THF. 2.0 ml 40% aqueous methylamine have been added at ambient temperature with stirring which was continued over night. After removal of the solvent in vacuo the mixture was purified by chromatography on silica with a heptane/ethyl acetate gradient. 90 mg of the desired Z-isomer have been collected.
  • 1H-NMR (CDCl3): δ=2.03 (s); 2.85 (d); 3.97 (s); 4.64 (s); 5.87 (s); 6.02 (d); 6.65 (br); 7.35 (d); 7.50 (d); 7.67 (d).
    • Example 5: Methyl N—[(Z)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-1-methyl-prop-1-enyl]-N-methoxy-carbamate (I-1)
  • Figure US20180360041A1-20181220-C00216
    • Ex. 5a: Cis-3-methyloxiran-2-yl]methanol (15)
  • To 10.0 g (138.7 mmol) Z-but-2-en-1-ol in 140 ml dichloromethane (DCM) 37.6 g (152.6 mmol) 3-chloroperbenzoic acid (70% purity) have been added at 0-5° C. in small portions with stirring. Stirring was continued at 0° C. for 2 h. 35.0 g calcium hydroxide have been added at 0-5° C. with stirring which was continued for about 2 h at 0° C. The precipitate was filtered off, washed with DCM, and the filtrates dried with sodium sulfate. The solvent was largely removed at 380 mbar/30° C. The crude product (15.0 g, purity 75%) was used without further purification.
    • Ex. 5b: Racemic 1-(4-chlorophenyl)-3-[[(2R,3S)-3-methyloxiran-2-yl]methoxy]pyrazole (16)
  • To 28.3 g (107.9 mmol) triphenylphosphine and 15.0 g (127.7 mmol) cis-3-methyloxiran-2-yl]methanol (15) from the preceding experiment in 400 ml THF have been added with stirring at −75° C. 22.9 g (113.0 mmol) azodicarbonic acid diisopropyl ester. The mixture has been stirred at this temperature for 5 min. Then 20.0 g (102.8 mmol) 1-(4-chlorophenyl)-3-hydroxypyrazole have been added with stirring at −70° C. The mixture was allowed to warm up to ambient temperature and stirred for about 1 d. After removal of the solvents in vacuo the crude product was stirred with 200 ml of diisopropylether from which 42 g of a solid substance have been collected and further purified by chromatography on 330 g silica with MTBE/heptane. Yield 22.5 g (82%).
    • Ex. 5c: 5-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methoxy-4-methyl-oxazolidin-2-one (17)
  • To 1.08 g (10.0 mmol) methyl N-methoxycarbamate in 17 ml DMSO have been added with stirring at ambient temperature 1.00 g (8.9 mmol) potassium tert.-butylate. Stirring has been continued for 5 min before 2.00 g (7.56 mmol) 1-(4-chlorophenyl)-3-[[(2R,3S)-3-methyloxiran-2-yl]methoxy]pyrazole have been added. The mixture was stirred at 90° C. for 20 h. After cooling to ambient temperature the reaction mixture was poured into 150 ml of water, extracted thrice with 30 ml ethyl acetate each, the combined extracts have been dried with sodium sulfate and the solvent removed in vacuo. The crude product (2.5 g) was used without further purification.
    • Ex. 5d: Racemic (2S,3R-1-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-3-(methoxyamino)butan-2-ol (18)
  • To 10.0 g (30.0 mmol) 5-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methoxy-4-methyl-oxazolidin-2-one in 100 ml ethanol has been added at ambient temperature with stirring 14.6 g (40.0 mmol) 21% sodium ethylate solution (in ethanol) and stirred over night. The solvent was largely removed in vacuo and the remaining mixture poured into 250 ml aqueous sodium dihydrogenphosphate solution, extracted thrice with 150 ml ethyl acetate each, dried with sodium sulfate to yield 8.7 g of an oil after evaporation of the solvent in vacuo. Further purified by chromatography on 120 g silica with MTBE/heptane. Yield 4.0 g (43%). 1H-NMR (CDCl3): δ=1.22 (d); 3.17 (m); 3.57 (s); 3.91 (m); 4.33 (m); 4.47 (m); 5.93 (s); 7.35 (d); 7.52 (d); 7.68 (s).
    • Ex. 5e: Racemic methyl N-[(1R,2S)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-hydroxy-1-methyl-propyl]-N-methoxy-carbamate (19)
  • To 1.00 g (3.2 mmol) Racemic (2S,3R-1-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-3-(methoxyamino)butan-2-ol in 7 ml THF 0.28 g (3.5 mmol) sodium hydrogencarbonate has been added. Then 0.33 g (3.5 mmol) methyl chloroformate has been added dropwise with stirring at ambient temperature. Stirring has been continued over night. The reaction mixture was poured into 10 ml of water, extracted thrice with 10 ml MTBE each, the combined extracts dried with sodium sulfate, and the solvent removed in vacuo. The crude product (1.3 g) was used without further purification.
    • Ex. 5f: Methyl N—[(Z)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-1-methyl-prop-1-enyl]-N-methoxy-carbamate (I-1)
  • To 3.50 g (9.46 mmol) racemic methyl N-[(1R,2S)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-hydroxy-1-methyl-propyl]-N-methoxy-carbamate in 13 ml THF 2.61 g (9.94 mmol) triphenylphoshin has been added with stirring at ambient temperature. The mixture was cooled to −15° C. Then 2.11 g (10.41 mmol) azodicarbonic acid diisopropyl ester has been added with stirring which was continued for 1 h at 0° C. and for about 1 d at ambient temperature. After removal of the solvents in vacuo the crude product was further purified by chromatography on 25 g silica with MTBE/heptane/1% triethylamine.
  • 1H-NMR (CDCl3): δ=1.93 (s); 3.72 (s); 3.81 (s); 4.78 (d); 5.73 (t); 5.90 (d); 7.36 (d); 7.55 (d); 7.70 (d).
  • TABLE I
    Compounds of formula I with physical data (melting point [° C.]; 1H-NMR (CDCl3)
    (δ); HPLC/MS retention time [min])
    No. R1 R2 R3 R4 X Y m.p. [° C.]; 1H-NMR (δ); Rt [min]
    I-1 CH3 H R3-1 R4-4, R5 = O Y-1 δ = 1.93 (s); 3.72 (s); 3.81 (s);
    OCH3 4.78 (d); 5.73 (t); 5.90 (d);
    7.36 (d); 7.55 (d); 7.70 (d)
    I-2 CH3 H R3-1 R4-4, R5 = NH Y-1
    OCH3
    I-3 CH3 H R3-1 R4-3 O Y-1
    I-4 CH3 H R3-1 R4-3 NH Y-1
    I-5 CH3 H R3-1 R4-1 O Y-1 88-89° C.
    I-6 CH3 H R3-1 R4-1 NH Y-1 130° C.
    I-7 CH3 H R3-1 R4-2 O Y-1 123-125° C.
    I-8 CH3 H R3-1 R4-2 NH Y-1
    I-9 CH3 H R3-1 R4-7 Y-1
    I-10 CH3 H R3-1 R4-4, R5 = O Y-1 δ = 1.90 (s); 3.05 (s); 3.70 (s);
    CH3 4.68 (m); 5.63 (m); 5.90 (d);
    7.35 (m); 7.55 (m); 7.68 (d)
    I-11 CH3 H R3-2 R4-1 NH Y-1 δ = 1.95 (s); 2.85 (d); 3.95 (s);
    4.55 (m); 5.87 (m); 5.95 (m);
    6.70 (br); 6.95 (m); 7.73 (m); 7.80 (m)
    I-12 CH3 H R3-3 R4-1 NH Y-1 δ = 1.95 (s); 2.27 (s); 2.80 (d);
    3.95 (s); 4.52 (m); 5.83 (d);
    5.93 (m); 6.75 (br); 6.95 (m); 7.30 (m)
    I-13 CH3 H R3-4 R4-1 NH Y-1 δ = 1.93 (s); 2.38 (s); 2.80 (d);
    3.95 (s); 4.55 (m); 5.88 (d);
    5.95 (m); 6.75 (br); 7.13 (m); 7.28 (m);
    7.41 (d); 7.64 (d)
    I-14 CH3 H R3-5 R4-1 NH Y-1 125-127° C.
    I-15 CH3 H R3-6 R4-1 NH Y-1 δ = 1.95 (s); 2.85 (d); 3.95 (s);
    4.55 (m); 5.90 (d); 5.95 (m);
    6.70 (br); 7.32 (m); 7.50 (s); 7.54 (d);
    7.70 (d)
    I-16 CH3 H R3-7 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.97 (s);
    4.56 (m); 5.88 (d); 5.94 (m);
    6.70 (br); 7.45 (m); 7.64 (s); 7.72 (d)
    I-17 CH3 H R3-8 R4-1 NH Y-1
    I-18 CH3 H R3-9 R4-1 NH Y-1 δ = 1.95 (s); 2.33 (s); 2.88 (d);
    3.97 (s); 4.56 (m); 5.85 (m);
    5.95 (m); 6.70 (br); 7.03 (t); 7.30 (m);
    7.44 (m); 7.62 (m)
    I-19 CH3 H R3-10 R4-1 NH Y-1
    I-20 CH3 H R3-11 R4-1 NH Y-1 δ = 1.95 (s); 2.25 (s); 2.30 (s);
    2.87 (d); 3.97 (s); 4.56 (m);
    5.85 (d); 5.95 (m); 6.73 (br); 7.15 (d);
    7.27 (m); 7.35 (d); 7.63 (d)
    I-21 CH3 H R3-12 R4-1 NH Y-1
    I-22 CH3 H R3-13 R4-1 NH Y-1
    I-23 CH3 H R3-14 R4-1 NH Y-1
    I-24 CH3 H R3-15 R4-1 NH Y-1
    I-25 CH3 H R3-16 R4-1 NH Y-1
    I-26 CH3 H R3-17 R4-1 NH Y-1
    I-27 CH3 H R3-14 R4-1 NH Y-1
    I-28 CH3 H R3-18 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.97 (s);
    4.57 (m); 5.87 (m); 5.95 (m);
    6.70 (br); 7.07 (m); 7.33 (m); 7.55 (m);
    7.64 (m)
    I-29 CH3 H R3-19 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.97 (s);
    4.58 (m); 5.88 (d); 5.94 (m);
    6.70 (br); 7.15 (m); 7.30 (m); 7.43 (m);
    7.64 (s); 7.70 (d)
    I-30 CH3 H R3-20 R4-1 NH Y-1
    I-31 CH3 H R3-21 R4-1 NH Y-1
    I-32 CH3 H R3-22 R4-1 NH Y-1 δ = 1.95 (s); 2.37 (s); 2.87 (d);
    3.95 (s); 4.55 (m); 5.86 (d);
    5.93 (m); 6.70 (br); 7.20 (m); 7.45 (m);
    7.65 (d)
    I-33 CH3 H R3-23 R4-1 NH Y-1 δ = 1.23 (m); 1.95 (s); 2.64 (m);
    2.87 (d); 3.95 (s); 4.58 (m);
    5.87 (d); 5.95 (m); 6.70 (br); 7.25 (m);
    7.48 (m); 7.67 (d)
    I-34 CH3 H R3-24 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.97 (s);
    4.58 (m); 5.92 (m); 6.70 (br);
    7.67 (m); 7.75 (d)
    I-35 CH3 H R3-25 R4-1 NH Y-1
    I-36 CH3 H R3-26 R4-1 NH Y-1
    I-37 CH3 H R3-58 R4-1 NH Y-1
    I-38 CH3 H R3-28 R4-1 NH Y-1
    I-39 CH3 H R3-29 R4-1 NH Y-1
    I-40 CH3 H R3-30 R4-1 NH Y-1
    I-41 CH3 H R3-31 R4-1 NH Y-1
    I-42 CH3 H R3-32 R4-1 NH Y-1
    I-43 CH3 H R3-33 R4-1 NH Y-1
    I-44 CH3 H R3-34 R4-1 NH Y-1
    I-45 CH3 H R3-35 R4-1 NH Y-1
    I-46 CH3 H R3-36 R4-1 NH Y-1
    I-47 CH3 H R3-37 R4-1 NH Y-1
    I-48 CH3 H R3-38 R4-1 NH Y-1
    I-49 CH3 H R3-39 R4-1 NH Y-1
    I-50 CH3 H R3-40 R4-1 NH Y-1
    I-51 CH3 H R3-41 R4-1 NH Y-1
    I-52 CH3 H R3-42 R4-1 NH Y-1
    I-53 CH3 H R3-43 R4-1 NH Y-1
    I-54 CH3 H R3-44 R4-1 NH Y-1
    I-55 CH3 H R3-45 R4-1 NH Y-1
    I-56 CH3 H R3-46 R4-1 NH Y-1
    I-57 CH3 H R3-47 R4-1 NH Y-1
    I-58 CH3 H R3-45 R4-1 NH Y-1
    I-59 CH3 H R3-49 R4-1 NH Y-1
    I-60 CH3 H R3-50 R4-1 NH Y-1
    I-61 CH3 H R3-51 R4-1 NH Y-1
    I-62 CH3 H R3-52 R4-1 NH Y-1
    I-63 CH3 H R3-53 R4-1 NH Y-1
    I-64 CH3 H R3-54 R4-1 NH Y-1
    I-65 CH3 H R3-55 R4-1 NH Y-1
    I-66 CH3 H R3-56 R4-1 NH Y-1
    I-67 CH3 H R3-57 R4-1 NH Y-1
    I-68 CH3 H R3-58 R4-4, R5 = O Y-1
    OCH3
    I-69 CH3 H R3-58 R4-4, R5 = NH Y-1
    OCH3
    I-70 CH3 H R3-58 R4-3 O Y-1
    I-71 CH3 H R3-58 R4-3 NH Y-1
    I-72 CH3 H R3-27 R4-1 O Y-1
    I-73 CH3 H R3-58 R4-2 O Y-1
    I-74 CH3 H R3-58 R4-2 NH Y-1
    I-75 CH3 H R3-58 R4-7 Y-1
    I-76 C2H5 H R3-1 R4-1 NH Y-1
    I-77 C2H5 H R3-2 R4-1 NH Y-1
    I-78 C2H5 H R3-58 R4-1 NH Y-1
    I-79 H CH3 R3-1 R4-1 NH Y-1 δ = 2.03 (s); 2.85 (d); 3.97 (s);
    4.64 (s); 5.87 (s); 6.02 (d);
    6.65 (br); 7.35 (d); 7.50 (d); 7.67 (d)
    I-80 H CH3 R3-1 R4-1 O Y-1
    I-81 CH3 H R3-1 R4-1 NH Y-3
    I-82 CH3 H R3-59 R4-1 NH Y-1 δ = 1.95 (s); 2.16 (s); 2.18 (s);
    2.30 (s); 2.90 (s); 3.97 (s);
    4.33 (m); 4.65 (m); 5.30 (m); 5.87 (m);
    6.07 (m); 6.55 (s); 6.65 (br);
    6.96 (s)
    I-83 CH3 H R3-60 R4-1 NH Y-1 δ = 1.95 (s); 2.22 (s); 2.90 (d);
    3.95 (s); 4.35 (m); 4.67 (m);
    5.30 (m); 5.88 (m); 6.07 (m); 6.65 (br);
    6.73 (d); 7.35 (d); 7.43 (s)
    I-84 CH3 H R3-61 R4-1 NH Y-1 δ = 1.95 (s); 2.15 (s); 2.18 (s);
    2.28 (s); 2.90 (d); 3.95 (s);
    4.33 (m); 4.67 (s); 5.39 (d); 5.43 (d);
    5.88 (m); 6.57 (s); 6.65 (br);
    6.95 (s)
    I-85 CH3 H R3-62 R4-1 NH Y-1 δ = 1.95 (s); 2.21 (s); 2.25 (s);
    2.89 (d); 3.95 (s); 4.35 (m);
    4.70 (s); 5.39 (d); 5.44 (d); 5.90 (m);
    6.65 (br); 6.73 (d); 7.40 (d);
    7.45 (s)
    I-86 CH3 H R3-63 R4-1 O Y-1 δ = 1.73 (m); 1.93 (s); 2.15 (s);
    2.30 (s); 3.85 (s); 4.05 (s);
    4.33 (m); 4.60 (m); 5.75 (m); 5.85 (m);
    6.55 (s); 6.95 (s)
    I-87 CH3 H R3-64 R4-1 O Y-1 δ = 1.95 (s); 2.12 (s); 2.14 (s);
    2.30 (s); 3.85 (s); 4.07 (s);
    4.35 (m); 4.63 (m); 5.85 (m); 6.15 (m);
    6.27 (m); 6.55 (s); 6.97 (s)
    I-88 CH3 H R3-65 R4-1 O Y-1 δ = 1.95 (s); 2.17 (s); 2.19 (s);
    3.85 (s); 4.05 (s); 4.35 (m);
    4.65 (m); 5.87 (m); 6.17 (m); 6.31 (m);
    6.72 (d); 7.35 (d); 7.43 (s).
    I-89 CH3 H R3-66 R4-1 NH Y-1 δ = 1.95 (s); 2.12 (s); 2.14 (s);
    2.30 (s); 2.90 (d); 3.95 (s);
    3.97 (s); 4.32 (m); 5.87 (m); 6.57 (s);
    6.65 (br); 6.97 (s)
    I-90 CH3 H R3-63 R4-1 NH Y-1 δ = 1.73 (m); 1.93 (s); 2.15 (s);
    2.30 (s); 2.90 (d); 3.95 (s);
    4.33 (m); 4.55 (m); 5.75 (m); 5.90 (m);
    6.57 (s); 6.65 (br); 6.95 (s)
    I-91 CH3 H R3-67 R4-1 NH Y-1 δ = 1.73 (m); 1.93 (s); 2.18 (s);
    2.20 (s); 2.90 (d); 3.95 (s);
    4.35 (m); 4.60 (m); 5.75 (m); 5.90 (m);
    6.55 (br); 6.73 (m); 7.35 (m);
    7.43 (s)
    I-92 CH3 H R3-64 R4-1 NH Y-1 δ = 1.95 (s); 2.15 (s); 2.30 (s);
    2.90 (d); 3.95 (s); 4.33 (m);
    4.60 (m); 5.87 (m); 6.15 (m); 6.27 (m);
    6.57 (s); 6.65 (br); 6.95 (s)
    I-93 CH3 H R3-65 R4-1 NH Y-1 δ = 1.95 (s); 2.19 (s); 2.21 (s);
    2.90 (d); 3.95 (s); 4.35 (m);
    4.65 (m); 5.90 (m); 6.17 (m); 6.31 (m);
    6.65 (br); 6.75 (d); 7.35 (m);
    7.43 (s)
    I-94 CH3 H R3-59 R4-1 O Y-1 δ = 1.95 (s); 2.15 (s); 2.30 (s);
    3.85 (s); 4.07 (s); 4.33 (m);
    4.63 (m); 5.30 (m); 5.87 (m); 6.07 (m);
    6.53 (s); 6.97 (s)
    I-95 CH3 H R3-60 R4-1 O Y-1 δ = 1.93 (s); 2.22 (s); 3.85 (s);
    4.07 (s); 4.37 (m); 4.67 (m);
    5.30 (m); 5.87 (m); 6.07 (m); 6.70 (d);
    7.37 (m); 7.45 (s)
    I-96 CH3 H R3-61 R4-1 O Y-1 δ = 1.95 (s); 2.15 (s); 2.17 (s);
    2.28 (s); 3.87 (s); 4.07 (s);
    4.33 (m); 4.67 (s); 5.40 (d); 5.43 (d);
    5.87 (m); 6.53 (s); 6.95 (s)
    I-97 CH3 H R3-62 R4-1 O Y-1 δ = 1.95 (s); 2.21 (s); 2.23 (s);
    3.85 (s); 4.05 (s); 4.37 (m);
    4.70 (s); 5.39 (d); 5.42 (d); 5.87 (m);
    6.70 (d); 7.38 (m); 7.45 (s)
    I-98 CH3 H R3-68 R4-1 O Y-1 δ = 1.23 (t); 1.87 (s); 2.08 (s);
    2.27 (s); 3.70 (s); 3.95 (s);
    4.10 (d); 4.30 (m); 5.90 (m); 6.65 (s);
    7.00 (s)
    I-99 CH3 H R3-69 R4-1 O Y-1
    I-100 CH3 H R3-69 R4-1 NH Y-1
    I-101 CH3 H R3-69 R4-4, R5 = O Y-1
    OCH3
    I-102 CH3 H R3-70 R4-1 O Y-6
    I-103 CH3 H R3-70 R4-1 NH Y-6
    I-104 CH3 H R3-70 R4-4, R5 = O Y-6
    OCH3
    I-105 CH3 H R3-71 R4-1 O Y-4
    I-106 CH3 H R3-71 R4-1 NH Y-4
    I-107 CH3 H R3-71 R4-4, R5 = O Y-4
    OCH3
    I-108 CH3 H R3-72 R4-1 NH Y-1
    I-109 CH3 H R3-72 R4-1 O Y-1
    I-110 CH3 H R3-72 R4-4, R5 = O Y-1
    OCH3
    I-111 CH3 H R3-72 R4-1 NH Y-2
    I-112 CH3 H R3-72 R4-1 O Y-2
    I-113 CH3 H R3-72 R4-4, R5 = O Y-2
    OCH3
    I-114 CH3 H R3-1 R4-4, R5 = O Y-2
    OCH3
    I-115 CH3 H R3-1 R4-4, R5 = NH Y-2
    OCH3
    I-116 CH3 H R3-1 R4-3 O Y-2
    I-117 CH3 H R3-1 R4-3 NH Y-2
    I-118 CH3 H R3-1 R4-1 O Y-2
    I-119 CH3 H R3-1 R4-1 NH Y-2
    I-120 CH3 H R3-1 R4-2 O Y-2
    I-121 CH3 H R3-1 R4-2 NH Y-2
    I-122 CH3 H R3-1 R4-7 Y-2
    I-123 CH3 H R3-1 R4-4, R5 = O Y-2
    CH3
    I-124 CH3 H R3-73 R4-1 NH Y-1
    I-125 CH3 H R3-74 R4-1 NH Y-1
    I-126 CH3 H R3-75 R4-1 NH Y-1
    I-127 CH3 H R3-76 R4-1 NH Y-1
    I-128 CH3 H R3-77 R4-1 NH Y-1
    I-129 CH3 H R3-78 R4-1 NH Y-1
    I-130 CH3 H R3-78 R4-1 NH Y-1
    I-131 CH3 H R3-80 R4-1 NH Y-1
    I-132 CH3 H R3-81 R4-1 NH Y-1
    I-133 CH3 H R3-82 R4-1 NH Y-1
    I-134 CH3 H R3-83 R4-1 NH Y-1
    I-135 CH3 H R3-84 R4-1 NH Y-1
    I-136 CH3 H R3-85 R4-1 NH Y-1
    I-137 CH3 H R3-86 R4-1 NH Y-1
    I-138 CH3 H R3-87 R4-1 NH Y-1
    I-139 CH3 H R3-88 R4-1 NH Y-1
    I-140 CH3 H R3-89 R4-1 NH Y-1
    I-141 CH3 H R3-90 R4-1 NH Y-1
    I-142 CH3 H R3-91 R4-1 NH Y-1
    I-143 CH3 H R3-92 R4-1 NH Y-1
    I-144 CH3 H R3-93 R4-1 NH Y-1
    I-145 CH3 H R3-94 R4-1 NH Y-1
    I-146 CH3 H R3-95 R4-1 NH Y-1
    I-147 CH3 H R3-96 R4-1 NH Y-1
    I-148 CH3 H R3-97 R4-1 NH Y-1
    I-149 CH3 H R3-98 R4-1 NH Y-1
    I-150 CH3 H R3-99 R4-1 NH Y-1
    I-151 CH3 H R3- R4-1 NH Y-1
    100
    I-152 CH3 H R3- R4-1 NH Y-1
    101
    I-153 CH3 H R3- R4-1 NH Y-1
    102
    I-154 CH3 H R3- R4-1 NH Y-1
    103
    I-155 CH3 H R3- R4-1 NH Y-1
    104
    I-156 CH3 H R3- R4-1 NH Y-1
    105
    I-157 CH3 H R3- R4-1 NH Y-1
    106
    I-158 CH3 H R3- R4-1 NH Y-1
    107
    I-159 CH3 H R3- R4-1 NH Y-1
    108
    I-160 CH3 H R3- R4-1 NH Y-1
    109
    I-161 CH3 H R3- R4-1 NH Y-1
    110
    I-162 CH3 H R3- R4-1 NH Y-1
    111
    I-163 CH3 H R3- R4-1 NH Y-1
    112
    I-164 CH3 H R3- R4-1 NH Y-1
    113
    I-165 CH3 H R3- R4-1 NH Y-1
    114
    I-166 CH3 H R3- R4-1 NH Y-1
    115
    I-167 CH3 H R3- R4-1 NH Y-1
    116
    I-168 CH3 H R3- R4-1 NH Y-1
    117
    I-169 CH3 H R3- R4-1 NH Y-4
    118
    I-170 CH3 H R3- R4-1 NH Y-4
    119
    I-171 CH3 H R3- R4-1 NH Y-4
    120
    I-172 CH3 H R3- R4-1 NH Y-4
    121
    I-173 CH3 H R3- R4-1 NH Y-4
    122
    I-174 CH3 H R3- R4-1 NH Y-4
    123
    I-175 CH3 H R3- R4-1 NH Y-4
    124
    I-176 CH3 H R3- R4-1 NH Y-4
    125
    I-177 CH3 H R3- R4-1 NH Y-1
    126
    I-178 CH3 OCH3 R3-1 R4-4, R5 = O Y-1
    OCH3
    I-179 CH3 OCH3 R3-1 R4-4, R5 = O Y-1
    OCH3
    I-180 CH3 OCH3 R3-1 R4-4, R5 = O Y-1
    OCH3
    I-181 CH3 H R3-1 R4-4, R5 = O Y-1
    OCH3
    I-182 CH3 H R3-1 R4-1 NH Y-1
    I-183 CH3 H R3-1 R4-1 O Y-1
    I-184 CH3 H R3-1 R4-2 NH Y-1
    I-185 CH3 H R3-1 R4-2 O Y-1
    I-186 CH3 H R3- R4-1 O Y-1 79-81° C.
    127
    I-187 CH3 H R3- R4-1 NH Y-1 δ = 1.95 (s); 2.12 (s); 2.18 (s);
    127 2.87 (d); 3.97 (s); 3.98 (s);
    4.35 (m); 5.90 (m); 6.65 (br); 7.35 (d);
    7.43 (s)
    I-188 C2H5 H R3-1 R4-1 O Y-1 δ = 1.05 (m); 2.30 (m); 3.85 (s);
    4.05 (s); 4.62 (m); 5.90 (m);
    7.35 (m); 7.52 (m); 7.70 (d)
    I-189 CH3 H R3- R4-4, R5 = O Y-1 δ = 1.90 (s); 2.22 (s); 2.24 (s);
    127 CH3 3.02 (s); 3.70 (s); 3.98 (s);
    4.48 (m); 5.57 (m); 6.75 (m); 7.40 (m);
    7.45 (s)
    I-190 CH3 H R3-66 R4-1 O Y-1 δ = 1.95 (s); 2.10 (s); 2.13 (s);
    2.30 (s); 3.85 (s); 3.92 (s);
    4.05 (s); 4.35 (m); 5.87 (m); 6.53 (s);
    6.97 (s)
    I-191 CH3 H R3- R4-1 O Y-1 δ = 1.30 (t); 1.95 (s); 2.20 (s);
    128 2.22 (s); 3.85 (s); 4.06 (s);
    4.20 (q); 4.37 (m); 5.87 (m); 6.71 (d);
    7.37 (m); 7.45 (s)
    I-192 CH3 H R3- R4-1 NH Y-1 δ = 1.30 (t); 1.95 (s); 2.20 (s);
    128 2.21 (s); 2.92 (d); 3.95 (s);
    4.22 (m); 4.37 (m); 5.90 (m); 6.65 (br);
    6.73 (m); 7.37 (m); 7.45 (s)
    I-193 CH3 H R3-68 R4-1 NH Y-1 δ = 1.32 (t); 1.95 (s); 2.16 (s);
    2.17 (s); 2.32 (s); 2.92 (d);
    3.97 (s); 4.20 (q); 4.33 (m); 5.90 (m);
    6.57 (s); 6.65 (br); 7.97 (s)
    I-194 CH3 H R3-5 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.05 (s);
    4.53 (m); 5.87 (d); 5.93 (m);
    7.07 (m); 7.25 (m); 7.55 (m); 7.63 (d)
    I-195 CH3 H R3-6 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.05 (s);
    4.55 (m); 5.88 (d); 5.93 (m);
    7.33 (m); 7.48 (s); 7.53 (d); 7.70 (d)
    I-196 CH3 H R3-2 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s);
    4.55 (m); 5.87 (d); 5.92 (m);
    6.95 (m); 7.73 (d); 7.80 (m)
    I-197 CH3 H R3-4 R4-1 O Y-1 δ = 1.95 (s); 2.37 (s); 3.85 (s);
    4.07 (s); 4.55 (m); 5.85 (d);
    5.92 (m); 7.12 (m); 7.28 (m); 7.43 (d);
    7.67 (d)
    I-198 CH3 H R3-22 R4-1 O Y-1 δ = 1.95 (s); 2.35 (s); 3.85 (s);
    4.05 (s); 4.57 (m); 5.83 (d);
    5.93 (m); 7.20 (d); 7.47 (d); 7.66 (d)
    I-199 CH3 H R3-24 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s);
    4.60 (m); 5.95 (m); 7.67 (m);
    7.77 (d)
    I-200 CH3 H R3-22 R4-1 O Y-1 δ = 1.25 (m); 1.95 (s); 2.65 (m);
    3.85 (s); 4.05 (s); 4.58 (m);
    5.83 (d); 5.93 (m); 7.25 (m); 7.48 (m);
    7.67 (d
    I-201 CH3 H R3-19 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s);
    4.58 (m); 5.87 (d); 5.93 (m);
    7.15 (m); 7.30 (m); 7.45 (m); 7.63 (s);
    7.70 (d)
    I-202 CH3 H R3-7 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s);
    4.58 (m); 5.90 (d); 5.95 (m);
    7.45 (m); 7.67 (d); 7.73 (d)
    I-203 CH3 H R3-129 R4-1 O Y-1 δ = 1.35 (d); 1.95 (s); 3.85 (s);
    4.07 (s); 4.55 (m); 5.84 (d);
    5.93 (m); 6.92 (m); 7.45 (m); 7.60 (d)
    I-204 CH3 H R3-11 R4-1 O Y-1 δ = 1.95 (s); 2.27 (s); 2.32 (s);
    3.85 (s); 4.07 (s); 4.58 (m);
    5.85 (d); 5.95 (m); 7.15 (d); 7.30 (m);
    7.37 (s); 7.66 (d)
    I-205 CH3 H R3-3 R4-1 O Y-1 δ = 1.95 (s); 2.25 (s); 3.83 (s);
    4.05 (s); 4.54 (m); 5.82 (d);
    5.92 (m); 6.95 (m); 7.25 (m); 7.32 (d)
    I-206 CH3 H R3-9 R4-1 O Y-1 δ = 1.93 (s); 2.31 (s); 3.85 (s);
    4.07 (s); 4.56 (m); 5.85 (m);
    5.95 (m); 7.03 (m); 7.33 (m); 7.43 (m);
    7.64 (m).
    I-207 CH3 H R3-18 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s);
    4.58 (m); 5.85 (d); 5.95 (m);
    7.05 (m); 7.33 (m); 7.55 (m); 7.65 (d)
    I-208 CH3 H R3-129 R4-1 NH Y-1 δ = 1.33 (d); 1.95 (s); 2.87 (d);
    3.97 (s); 4.55 (m); 5.84 (m);
    5.95 (m); 6.73 (br); 6.92 (d); 7.45 (d);
    7.62 (m)
    I-209 CH3 H R3-58 R4-1 O Y-1 δ = 1.95 (s); 3.83 (s); 4.05 (s);
    4.65 (m); 5.95 (m); 7.43 (d);
    7.55 (d); 8.23 (s)
    I-210 Cl CH3 R3-1 R4-1 NH Y-1 δ = 2.10 (s); 2.65 (d); 4.01 (s);
    4.95 (s); 5.97 (d); 6.85 (br);
    7.37 (d); 7.50 (d); 7.67 (d)
    I-211 phenyl ring* R3-1 R4-7 Y-1 90° C.
    R6 = CH3
    I-212 phenyl ring* R3-98 R4-7 Y-1 151° C.
    R6 = CH3
    I-213 phenyl ring* R3-130 R4-7 Y-4
    R6 = CH3
    I-214 phenyl ring* R3-131 R4-7 Y-4 139-142° C.
    R6 = CH3
    I-215 phenyl ring* R3-132 R4-7 Y-4 58-63° C.
    R6 = CH3
    I-216 phenyl ring* R3-133 R4-7 Y-1 111-113° C.
    R6 = CH3
    I-217 phenyl ring* R3-65 R4-7 Y-1 78-88° C.
    R6 = CH3
    I-218 phenyl ring* R3-60 R4-7 Y-1 83-88° C.
    R6 = CH3
    I-219 phenyl ring* R3-67 R4-7 Y-1 87-89° C.
    R6 = CH3
    I-220 phenyl ring* R3-62 R4-7 Y-1 82-88° C.
    R6 = CH3
    I-221 phenyl ring* R3-134 R4-7 Y-1 92-98° C.
    R6 = CH3
    I-222 phenyl ring* R3-135 R4-7 Y-1 141-145° C.
    R6 = CH3
    I-223 phenyl ring* R3-64 R4-7 Y-1 88-91° C.
    R6 = CH3
    I-224 phenyl ring* R3-59 R4-7 Y-1 82-86° C.
    R6 = CH3
    I-225 phenyl ring* R3-63 R4-7 Y-1 64-70° C.
    R6 = CH3
    I-226 phenyl ring* R3-136 R4-7 Y-1 101-108° C.
    R6 = CH3
    I-227 phenyl ring* R3-137 R4-7 Y-1 98-102° C.
    R6 = CH3
    I-228 phenyl ring* R3-138 R4-7 Y-1 71-75° C.
    R6 = CH3
    I-229 phenyl ring* R3-139 R4-7 Y-7 72-74° C.
    R6 = CH3
    I-230 phenyl ring* R3-140 R4-7 Y-7 δ = 1.65 (s); 3.32 (s); 3.67 (s);
    R6 = CH3 5.20 (s); 7.07 (m); 7.27 (m);
    7.47 (m)
    I-231 phenyl ring* R3-141 R4-7 Y-1 136-138° C.
    R6 = CH3
    I-232 phenyl ring* R3-142 R4-7 Y-7 δ = 1.65 (s); 3.43 (s); 3.70 (s);
    R6 = CH3 5.20 (s); 7.30-7.65 (m)
    I-233 phenyl ring* R3-127 R4-7 Y-1 Rt = 3.678 min
    R6 = CH3
    I-234 phenyl ring* R3-143 R4-7 Y-1 Rt = 4.092 min
    R6 = CH3
    I-235 phenyl ring* R3-144 R4-7 Y-1 Rt = 4.065 min
    R6 = CH3
    I-236 phenyl ring* R3-145 R4-7 Y-1 Rt = 3.947 min
    R6 = CH3
    I-237 phenyl ring* R3-146 R4-7 Y-1 Rt = 3.875 min
    R6 = CH3
    I-238 phenyl ring* R3-147 R4-7 Y-1 Rt = 4.100 min
    R6 = CH3
    I-239 phenyl ring* R3-68 R4-7 Y-1 Rt = 3.933 min
    R6 = CH3
    I-240 phenyl ring* R3-148 R4-7 Y-4 Rt = 3.496 min
    R6 = CH3
    I-241 phenyl ring* R3-149 R4-7 Y-4 Rt = 4.075 min
    R6 = CH3
    I-242 phenyl ring* R3-150 R4-7 Y-1 Rt = 4.128 min
    R6 = CH3
    I-243 phenyl ring* R3-151 R4-7 Y-1 Rt = 3.894 min
    R6 = CH3
    I-244 phenyl ring* R3-152 R4-7 Y-1 Rt = 3.875 min
    R6 = CH3
    I-245 phenyl ring* R3-153 R4-7 Y-1 Rt = 3.995 min
    R6 = CH3
    I-246 phenyl ring* R3-154 R4-7 Y-1 Rt = 4.115 min
    R6 = CH3
    I-247 phenyl ring* R3-20 R4-7 Y-1 Rt = 3.715 min
    R6 = CH3
    I-248 phenyl ring* R3-157 R4-7 Y-1 Rt = 3.714 min
    R6 = CH3
    I-249 phenyl ring* R3-128 R4-7 Y-1 Rt = 3.861 min
    R6 = CH3
    I-250 phenyl ring* R3-158 R4-7 Y-1 Rt = 4.251 min
    R6 = CH3
    I-251 phenyl ring* R3-159 R4-7 Y-1 105-107° C.
    R6 = CH3
    I-252 phenyl ring* R3-151 R4-7 Y-1 102-104° C.
    R6 = Ethyl
    I-253 phenyl ring* R3-1 R4-7 Y-1 96-97° C.
    R6 = CHF2
    I-254 phenyl ring* R3-128 R4-7 Y-1 Rt = 4.219 min
    R6 = Ethyl
    I-255 phenyl ring* R3-68 R4-7 Y-1 Rt = 4.239 min
    R6 = Ethyl
    I-256 phenyl ring* R3-146 R4-7 Y-1 Rt = 4.176 min
    R6 = Ethyl
    I-257 phenyl ring* R3-66 R4-7 Y-1 Rt = 4.013 min
    R6 = Ethyl
    I-258 phenyl ring* R3-160 R4-7 Y-1 δ = 2.15 (s); 3.67 (s); 3.95 (s);
    R6 = CH3 5.28 (s); 6.85 (m); 7.45 (m);
    7.50 (m); 7.70 (m)
    I-259 phenyl ring* R3-161 R4-7 Y-1 δ = 1.33 (t); 2.17 (s); 3.68 (s);
    R6 = CH3 4.22 (q); 5.28 (s); 6.87 (d);
    7.45 (m); 7.52 (m); 7.73 (m)
    I-260 phenyl ring* R3-162 R4-7 Y-1 Rt = 3.924 min
    R6 = CH3
    I-261 phenyl ring* R3-163 R4-7 Y-1 Rt = 4.131 min
    R6 = CH3
    I-262 phenyl ring* R3-164 R4-7 Y-1 Rt = 4.141 min
    R6 = CH3
    I-263 phenyl ring* R3-165 R4-7 Y-1 Rt = 3.916 min
    R6 = CH3
    I-264 phenyl ring* R3-166 R4-7 Y-1 Rt = 4.220 min
    R6 = CH3
    I-265 phenyl ring* R3-167 R4-7 Y-1 Rt = 4.050 min
    R6 = CH3
    I-266 phenyl ring* R3-149 R4-7 Y-8 δ = 2.03 (s); 3.71 (s);
    R6 = CH3 7.45-7.62 (m)
    I-267 phenyl ring* R3-168 R4-7 Y-1 δ = 2.20 (s); 2.40 (s); 3.69 (s);
    R6 = CH3 5.20 (s); 6.70 (s); 7.12 (s);
    7.42 (s); 7.53 (m); 7.72 (m); 7.91 (s)
    I-268 phenyl ring* R3-169 R4-7 Y-1 δ = 2.11 (s); 2.18 (s); 3.62 (s);
    R6 = CH3 3.72 (s); 5.21 (s); 6.77 (s);
    6.96 (s); 7.25 (s); 7.53 (m); 7.72 (m);
    8.91 (s)
    I-269 phenyl ring* R3-170 R4-7 Y-1 δ = 2.00 (s); 2.05 (s); 2.16 (s);
    R6 = CH3 2.21 (s); 3.70 (s); 5.16 (s);
    6.72 (s); 6.82 (s); 7.50 (m); 7.74 (m)
    I-270 phenyl ring* R3-171 R4-7 Y-1 δ = 2.16 (s); 2.39 (s); 2.53 (s);
    R6 = CH3 3.70 (s); 5.19 (s); 6.70 (s);
    7.53 (m); 7.72 (m)
    I-271 phenyl ring* R3-172 R4-7 Y-1 δ = 2.18 (s); 2.29 (s); 3.70 (s);
    R6 = CH3 5.18 (s); 6.71 (s); 7.06 (s);
    7.50 (m); 7.71 (m); 8.38 (s); 8.44 (s)
    I-272 phenyl ring* R3-173 R4-7 Y-1 δ = 1.28 (m); 2.12 (s);
    R6 = CH3 3.00 (broad); 3.58 (m); 3.69 (s);
    5.52 (s); 6.28 (s); 7.45 (m); 7.72 (m)
    I-273 phenyl ring* R3-174 R4-7 Y-1 δ = 0.97 (m); 1.02 (m); 1.20 (m);
    R6 = CH3 1.90 (m); 2.05 (s); 2.62 (m);
    3.68 (s); 5.51 (s); 5.84 (s); 7.50 (m);
    7.73 (m)
    I-274 phenyl ring* R3-175 R4-7 Y-8 Rt = 3.715 min
    R6 = CH3
    I-275 CH3 H R3-20 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s);
    4.58 (m); 5.92 (m); 7.45 (m);
    7.52 (m); 7.75 (m); 7.84 (d)
    I-276 CH3 H R3-12 R4-1 O Y-1 72-74° C.
    I-277 CH3 H R3-15 R4-1 O Y-1 73-75° C.
    I-278 CH3 H R3-176 R4-1 O Y-1 δ = 1.97 (s); 3.85 (s); 4.07 (s);
    4.58 (d); 5.90 (d); 5.95 (m);
    7.17 (t); 7.43 (m); 7.65 (m)
    I-279 CH3 H R3-98 R4-1 O Y-1 90-92° C.
    I-280 CH3 H R3-20 R4-1 NH Y-1 101-103° C.
    I-281 CH3 H R3-12 R4-1 NH Y-1 112-115° C.
    I-282 CH3 H R3-15 R4-1 NH Y-1 93-95° C.
    I-283 CH3 H R3-176 R4-1 NH Y-1 84-86° C.
    I-284 CH3 H R3-98 R4-1 NH Y-1 δ = 1.95 (s); 2.27 (s); 2.93 (d);
    3.97 (s); 4.48 (m); 5.93 (m);
    6.42 (m); 6.67 (broad); 6.80 (d);
    7.37 (d); 7.45 (m); 7.68 (m); 7.83 (m)
    I-285 CH3 H R3-1 R4-4, R5 = O Y-1 δ = 1.93 (s); 3.72 (s); 3.81 (s);
    OCH3 4.78 (d); 5.73 (t); 5.90 (d);
    7.36 (d); 7.55 (d); 7.70 (d)
    I-286 CH3 H R3-51 R4-1 O Y-1 δ = 1.93 (s); 2.45 (s); 3.82 (s);
    4.05 (s); 4.60 (d); 5.92 (t);
    7.25-7.50 (m)
    I-287 C2H5 H R3-1 R4-1 NH Y-1 δ = 1.05 (t); 2.30 (q); 2.90 (d);
    3.97 (s); 4.58 (m); 5.93 (m);
    6.70 (broad); 7.35 (m); 7.53 (m);
    7.68 (s)
    I-288 CH3 H R3-58 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.97 (s);
    4.63 (m); 5.95 (m); 6.75 (broad);
    7.43 (m); 7.55 (m); 8.23 (s)
    I-289 CH3 H R3-51 R4-1 NH Y-1 δ = 1.93 (s); 2.45 (s); 2.83 (d);
    3.95 (s); 4.58 (m); 5.92 (m);
    6.73 (broad); 7.30-7.50 (m)
    I-290 CH3 H R3-1 R4-4, R5 = O Y-1 δ = 1.18 (m); 1.95 (s);
    C2H5 3.45 (broad); 3.73 (s); 4.67 (m);
    5.70 (m); 5.90 (m); 7.35 (m); 7.53 (m);
    7.67 (m)
    I-291 CH3 H R3-39 R4-1 O Y-1 72° C.
    I-292 CH3 H R3-44 R4-1 O Y-1 106-110° C.
    I-293 CH3 H R3-44 R4-1 NH Y-1 177° C.
    I-294 CH3 H R3-177 R4-1 O Y-1 δ = 1.93 (s); 3.20 (m); 3.28 (m);
    3.83 (s); 3.90 (m); 4.05 (s);
    4.42 (m); 4.50 (m); 5.88 (m); 5.94 (s);
    6.83 (m); 7.25 (m); 7.50 (s)
    I-295 CH3 H R3-39 R4-1 NH Y-1 142° C.
    I-296 Iso- H R3-1 R4-1 O Y-1 δ = 0.93 (m); 1.60 (m); 2.15 (d);
    butyl 3.84 (s); 4.07 (s); 4.62 (m);
    5.89 (m); 7.35 (d); 7.53 (d); 7.67 (s)
    I-297 CH3 H R3-29 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s);
    4.65 (m); 5.95 (m); 7.27 (m);
    7.87 (m); 8.35 (s)
    I-298 CH3 H R3-36 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s);
    4.65 (m); 5.95 (m); 7.63 (m);
    7.67 (m); 7.93 (s); 8.37 (s)
    I-299 Iso- H R3-1 R4-1 NH Y-1 177° C.
    butyl
    I-300 C2H5 H R3-58 R4-1 O Y-1 87° C.
    I-301 CH3 H R3-29 R4-1 NH Y-1 140° C.
    I-302 CH3 H R3-36 R4-1 NH Y-1 125° C.
    I-303 CH3 H R3-33 R4-1 O Y-1 δ = 1.95 (s); 3.83 (s); 4.05 (s);
    4.65 (m); 5.95 (m); 7.37 (m);
    7.57 (m); 8.27 (s)
    I-304 CH3 H R3-54 R4-1 O Y-1 δ = 1.25 (m); 1.95 (s); 2.68 (m);
    3.83 (s); 4.05 (s); 4.65 (m);
    5.95 (m); 7.30 (m); 7.51 (m); 8.20 (s)
    I-305 CH3 H R3-33 R4-1 NH Y-1 126° C.
    I-306 CH3 H R3-54 R4-1 NH Y-1 128° C.
    I-307 CH3 H R3-178 R4-1 O Y-1 δ = 1.95 (s); 2.27 (s); 3.82 (s);
    4.07 (s); 4.62 (m); 5.95 (m);
    7.28 (m); 7.36 (m); 7.93 (s)
    I-308 CH3 H R3-130 R4-1 O Y-4 δ = 1.95 (s); 2.25 (s); 3.80 (s);
    4.05 (s); 4.55 (m); 5.90 (m);
    7.25-7.60 (m); 7.77 (m); 7.85 (s);
    8.05 (s); 8.27 (s)
    I-309 CH3 H R3-130 R4-1 NH —CH═N—O—CH2 − δ = 1.95 (s); 2.88 (d); 3.96 (s);
    4.50 (m); 5.92 (m); 6.70 (broad);
    7.25-7.60 (m); 7.76 (m); 8.05 (s);
    8.08 (s); 8.27 (s)
    I-310 CH3 H R3-42 R4-1 O Y-1 116° C.
    I-311 C2H5 H R3-58 R4-1 NH Y-1 154° C.
    I-312 CH3 H R3-30 R4-1 NH Y-1 167° C.
    I-313 CH3 H R3-178 R4-1 NH Y-1 143° C.
    I-314 CH3 H R3-42 R4-1 NH Y-1 147° C.
    I-315 CH3 H R3-40 R4-1 NH Y-1 153° C.
    I-316 CH3 H R3-177 R4-1 NH Y-1 δ = 1.93 (s); 2.88 (d); 3.20 (m);
    3.28 (m); 3.90 (m); 3.95 (s);
    4.42 (m); 4.50 (m); 5.90 (m); 5.95 (s);
    6.67 (broad); 6.86 (m); 7.25 (m);
    7.50 (s)
    I-317 CH3 H R3-179 R4-1 NH Y-1 δ = 1.83 (s); 1.93 (s); 2.18 (s);
    2.42 (m); 2.70 (m); 2.88 (d);
    3.83 (s); 3.95 (s); 4.35 (m); 5.90 (m);
    6.65 (m); 6.93 (m)
    I-318 CH3 H R3-38 R4-1 O Y-1 87° C.
    I-319 CH3 H R3-32 R4-1 O Y-1 δ = 1.93 (s); 2.27 (s); 3.80 (s);
    4.05 (s); 4.62 (m); 5.95 (m);
    7.30 (m); 7.93 (s)
    I-320 CH3 H R3-34 R4-1 NH Y-1 120° C.
    I-321 CH3 H R3-38 R4-1 NH Y-1 143° C.
    I-322 CH3 H R3-37 R4-1 NH Y-1 117° C.
    I-323 CH3 H R3-40 R4-1 O Y-1 118° C.
    I-324 CH3 H R3-37 R4-1 O Y-1 δ = 1.93 (s); 2.23 (s); 2.35 (s);
    3.80 (s); 4.05 (s); 4.62 (m);
    5.95 (m); 7.15 (m); 7.91 (s)
    I-325 CH3 H R3-43 R4-1 NH Y-1 136° C.
    I-326 CH3 H R3-34 R4-1 O Y-1 δ = 1.95 (s); 3.83 (s); 4.05 (s);
    4.63 (m); 5.95 (m); 7.67 (m);
    7.82 (m); 8.42 (s)
    I-327 CH3 H R3-32 R4-1 NH Y-1 δ = 2.07 (s); 2.42 (s); 2.92 (d);
    4.08 (s); 4.78 (m); 6.08 (m);
    6.93 (broad); 7.45 (m); 8.08 (s)
    I-328 CH3 H R3-41 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.95 (s);
    4.65 (m); 5.93 (m); 6.73 (broad);
    7.30 (m); 7.55 (m); 8.23 (s)
    I-329 CH3 H R3-28 R4-1 NH Y-1 94° C.
    I-330 CH3 H R3-50 R4-1 NH Y-1 130° C.
    I-331 CH3 H R3-41 R4-1 O Y-1 δ = 1.95 (s); 3.87 (s); 4.06 (s);
    4.63 (m); 5.93 (m); 7.32 (m);
    7.55 (m); 8.23 (s)
    I-332 C2H5 H R3-2 R4-1 O Y-1 δ = 1.05 (t); 2.30 (m); 3.82 (s);
    4.05 (s); 4.62 (d); 5.90 (m);
    6.93 (m); 7.73 (m); 7.80 (m)
    I-333 CH3 H R3-180 R4-1 O Y-1 δ = 1.95 (s); 2.27 (s); 3.85 (s);
    4.07 (s); 4.40 (m); 5.88 (m);
    6.66 (d); 6.78 (m); 7.37 (m); 7.45 (m);
    7.83 (d)
    I-334 CH3 H R3-77 R4-1 O Y-1 123-124° C.
    I-335 CH3 H R3-119 R4-1 O Y-4 δ = 1.90 (s); 2.12 (s); 3.83 (s);
    3.92 (s); 4.03 (s); 4.33 (m);
    5.74 (m); 7.18-7.45 (m)
    I-336 CH3 H R3-80 R4-1 O Y-1 133-134° C.
    I-337 CH3 H R3-180 R4-1 NH Y-1 δ = 1.95 (s); 2.27 (s); 2.90 (d);
    3.97 (s); 4.40 (m); 5.88 (m);
    6.66 (broad); 6.82 (m); 7.37 (m);
    7.45 (m); 7.81 (d)
    I-338 CH3 H R3-79 R4-1 O Y-1 94-97° C.
    I-339 CH3 H R3-119 R4-1 NH Y-4 δ = 1.90 (s); 2.12 (s); 2.85 (d);
    3.92 (s); 4.33 (m); 5.75 (m);
    6.60 (broad); 7.18-7.45 (m)
    I-340 CH3 H R3-130 R4-1 O —CH═N—O—CH2 − δ = 1.95 (s); 3.82 (s); 4.05 (s);
    4.52 (m); 5.87 (m); 7.25-7.60 (m);
    7.75 (m); 7.80 (s); 8.05 (s);
    8.26 (s)
    I-341 CH3 H R3-130 R4-1 NH Y-4 δ = 1.95 (s); 2.25 (s); 2.83 (d);
    3.97 (s); 4.54 (m); 5.93 (m);
    6.75 (broad); 7.25-7.60 (m); 7.77 (m);
    7.82 (s); 8.02 (s); 8.29 (s)
    I-342 CH3 H R3-181 R4-1 NH Y-1 δ = 1.95 (s); 2.27 (s); 2.88 (d);
    3.97 (s); 4.39 (m); 5.93 (m);
    6.67 (broad); 6.80 (m); 7.08 (m);
    7.27 (m); 7.45 (m)
    I-343 CH3 H R3-182 R4-1 NH Y-1 δ = 1.95 (s); 2.27 (s); 2.91 (d);
    3.98 (s); 4.41 (m); 5.93 (m);
    6.70 (broad); 6.85 (m); 7.37 (m);
    7.65 (m)
    I-344 CH3 H R3-183 R4-1 NH Y-1 δ = 1.95 (s); 2.25 (s); 2.91 (d);
    3.98 (s); 4.40 (m); 5.93 (m);
    6.66 (broad); 6.83 (m); 7.25-7.46 (m)
    I-345 CH3 H R3-184 R4-1 NH Y-1 δ = 1.95 (s); 2.25 (s); 2.90 (d);
    3.85 (s); 3.98 (s); 4.38 (m);
    5.93 (m); 6.66 (broad); 6.82 (m);
    7.30 (m)
    I-346 CH3 H R3-185 R4-1 NH Y-1 δ = 1.95 (s); 2.20 (s); 2.88 (d);
    3.95 (s); 4.30 (m); 4.98 (s);
    5.92 (m); 6.65 (m); 6.80 (m); 7.40 (m)
    I-347 CH3 H R3-69 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.95 (s);
    4.65 (m); 5.92 (m); 6.67 (broad);
    6.87 (m); 7.25 (m); 7.67 (m)
    I-348 CH3 H R3-186 R4-1 NH Y-1 δ = 1.42 (m); 1.95 (s); 2.27 (s);
    2.91 (d); 2.96 (m); 3.98 (s);
    4.42 (m); 5.93 (m); 6.70 (broad);
    6.83 (m); 7.87 (m)
    I-349 C2H5 H R3-5 R4-1 NH Y-1 98° C.
    I-350 CH3 H R3-88 R4-1 O Y-1 δ = 1.95 (s); 3.53 (s); 3.85 (s);
    4.05 (s); 4.50 (m); 5.65 (s);
    5.90 (m); 7.28 (m); 7.50 (s)
    I-351 CH3 H R3-88 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.50 (s);
    3.97 (s); 4.48 (m); 5.65 (m);
    5.93 (m); 6.70 (broad); 7.28 (m);
    7.50 (s)
    I-352 CH3 H R3-76 R4-1 NH Y-1 δ = 1.95 (s); 2.27 (s); 2.87 (d);
    3.95 (s); 4.63 (m); 5.93 (m);
    6.66 (broad); 7.35 (m); 7.77 (m)
    I-353 CH3 H R3-187 R4-1 NH Y-1 δ = 1.95 (s); 2.87 (d); 3.97 (s);
    4.63 (m); 5.90 (d); 5.95 (m);
    6.70 (broad); 7.48 (m); 7.85 (m);
    7.97 (d)
    I-354 CH3 H R3-188 R4-1 NH Y-1 δ = 1.93 (s); 2.77 (d); 3.93 (s);
    4.54 (m); 5.92 (m); 6.80 (broad);
    7.33 (m); 7.45 (m)
    I-355 CH3 H R3-189 R4-1 NH Y-1 δ = 1.95 (s); 2.85 (d); 3.95 (s);
    4.55 (m); 5.92 (m); 6.70 (broad);
    7.23 (m); 7.40 (m); 7.64 (s);
    7.78 (d)
    I-356 CH3 H R3-193 R4-1 NH Y-1 δ = 1.94 (s); 2.87 (d); 3.94 (s);
    4.44 (m); 5.17 (s); 5.67 (d);
    5.88 (m); 6.70 (broad); 6.86 (m);
    7.20 (m); 7.37 (d)
    I-357 CH3 H R3-194 R4-1 NH Y-1 δ = 1.95 (s); 2.80 (d); 3.95 (s);
    4.55 (m); 5.87 (d); 5.93 (m);
    6.75 (broad); 7.25 (m); 7.35 (m);
    7.45 (m); 7.55 (m); 7.70 (d)
    I-358 CH3 H R3-83 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.95 (s);
    4.57 (m); 5.92 (m); 6.13 (s);
    6.83 (broad); 7.45 (m); 7.35 (m);
    7.70 (m)
    I-359 CH3 H R3-195 R4-1 NH Y-1 δ = 1.95 (s); 2.50 (s); 2.88 (d);
    3.95 (s); 4.57 (m); 5.85 (d);
    5.95 (m); 6.70 (broad); 6.90 (m);
    7.60 (m); 8.33 (d)
    *“phenyl ring” denotes that R1 and R2 together with the two carbon atoms linking them form a phenyl ring.
    Isobutyl = 2-methyl-1-propyl.
    m.p. = melting point;
    Rt = HPLC Retention time.
    HPLC-data: RP-18 column (Chromolith Speed ROD 50 × 4.6 mm from Merck KgaA, Germany), 1.8 ml/min, injection volume 2 μl, column temperature 40° C.
    Eluent: Acetonitrile + 0.1% trifluoroacetic acid (TFA)/water + 0.1% TFA (gradient %:95 to 95:5 within 5 min), 40° C. MS: Quadrupole electrospray ionisation, 80 V (pos. mode).
    • II. EXAMPLES OF THE ACTION AGAINST HARMFUL FUNGI
  • The fungicidal action of the compounds of the formula I was demonstrated by the following experiments:
    • II.1 Microtiter Tests
  • The active substances were formulated separately as a stock solution in dimethyl sulfoxide (DMSO) at a concentration of 10 000 ppm.
    • Use Example 1: Activity Against the Septoria Blotch Pathogen Caused by Septoria tritici in the Microtiter Test Fungal Strains Used:
  • a) Septoria tritici (Qo-inhibitor sensitive, wild-type)
  • b) Septoria tritici (Qo-inhibitor-resistant, G143A mutant)
  • 100 ml 2% Malt extract in water at pH6.8 were inoculated with microspores from 2 week old cultures grown on 2% malt extract+2% agar in Petri dishes and incubated for 3 days on a rotary shaker at 24° C. and 150 rpm. The culture was harvested, glycerol was added (15% (v/v) and kept frozen at −20° C. in aliquots of 1 ml.
  • 1 ml stock suspension was thawed and suspended into 800 ml of 2% malt extract in water at pH 6.8. Compounds were diluted from stock solution in (dimethylsulfoxide) DMSO in 10 steps. The compound solutions were diluted ⅕ with sterile deionized water before use. 5 μl of the compound solutions were transferred into empty microplates. The plates were then filled with 195 μl of the microspore suspension of each strain.
  • The antifungal activity was determined by measuring the turbidity of a culture in 96-well microplates in the presence of test compounds. Fungal growth was measured by recording the optical density at 620 nm every 15 h for 150 h. The relative antifungal activity was calculated by comparison of the effect of the test compounds with the effect of a DMSO control and a standard fungicide.
  • IC50-values (concentration of test compound resulting in 50% inhibition of fungal growth) were calculated from the resulting dose-response for each compound and strain. The initial concentration of the test compounds and the 10 steps of dilution (1:4 each) allowed IC50-values from 0.001 to 100 μmol/l (μM) to be assessed.
  • TABLE II
    Resistant Septoria Sensitive Septoria Resistance
    tritici isolate tritici isolate factor
    (G143A mutation) (wild type) RF = R-
    Compound (R-IC50) [μM] (S-IC50) [μM] IC50/S-IC50
    Azoxystrobin >100 3.5 n.d.
    Dimoxystrobin >100 7.1 n.d.
    Enestroburin >100 4.5 n.d.
    Kresoximmethyl >100 0.76 n.d.
    Metominostrobin >100 >100 n.d.
    Orysastrobin >100 27 n.d.
    Picoxystrobin >100 2.3 n.d.
    Pyrametostrobin >100 >100 n.d.
    Pyraoxystrobin >100 1.6 n.d.
    Pyraclostrobin 3.4 0.0012 2882
    Trifloxystrobin >100 0.52 n.d.
    I-5 2.2 0.083 26
    I-6 8.3 0.34 24
    I-82 6.8 1.1 6
    I-83 7.6 1.6 4.6
    I-84 16.1 0.5 33
    I-85 22 0.8 29
    I-90 26 1.0 26
    I-91 27 1.6 17
    I-94 12 0.6 22
    I-95 29 2.2 14
    I-97 49 1.7 29
    I-191 37 1.3 29
    I-211 1.1 0.44 2.6
    I-212 8.3 1.4 6
    I-213 0.057 0.076 0.7
    I-215 48 1.7 28
    I-216 12.0 6.3 2.0
    I-217 63 6.3 10
    I-218 79 5.6 14
    I-221 10 3.4 3
    I-223 19 2.7 7
    I-224 5.4 1.7 3.2
    I-225 72 3.4 21
    I-228 10 3.4 3.0
    I-230 25 3.2 8
    I-233 2.7 0.24 12
    I-234 4 2.4 1.7
    I-235 51 13 4
    I-236 24 6 4
    I-238 12 6 1.9
    I-243 15 4.1 3.6
    I-244 1.3 0.6 2.0
    I-247 9 5 1.9
    I-249 11 2.4 5
    I-250 97 19 5
    I-255 42 19 2.2
    I-256 24 21 1.1
    I-257 67 15 4.5
    I-260 3.3 2.3 1.4
    I-261 5 2.9 1.6
    I-262 1.6 1 1.6
    I-265 4 3.8 1.1
    I-267 5 2.9 1.7
    I-269 74 8 10
    I-270 57 6 10
    I-271 7 1.9 3.9
    I-273 22 5 4
    I-274 19 9 2.0
    I-287 18 1.5 12
    I-288 28 3.5 8.0
    I-291 18 1.0 18.0
    I-292 33 7.9 4.2
    I-298 31 3.6 8.6
    I-303 4.6 0.27 17.0
    I-304 9.1 0.53 17.2
    I-305 32 9.3 3.4
    I-307 67 19.0 3.5
    I-310 11 0.39 28.2
    I-319 102 17.0 6.0
    I-324 38 1.9 20.0
    I-326 18 1.2 15.0
    I-331 25 1.8 13.9
    I-339 21 1.0 21.0
  • While commercial strobilurine type fungicides are do not show any activity against the resistant Septoria strain, containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors (G143A) while being active against sensitive wild type strains, compounds I have been active against both, the resistant and the wild-type strains. In general, the resistance factor ratio (RF) calculated from the IC50 values determined for both Septoria strains, was below 30 for the compounds I according to the invention. However, resistance factor ratios for commercial strobilurine type compounds are in most cases greater than 100 and usually greater than several hundreds (for details see e.g. FRAC, Mutations associated with QoI-resistance, December 2006; http://frac.info/frac/work/Mutations%20associated%20with%20QoI%20resistance.pdf and citations cited therein).
    • II.2 Comparative Examples A) Field Trials Compounds Used:
  • Compound I-6 was used as 50 g/l EC formulation. Pyraclostrobin was used as commercial product HEADLINE.
  • Compounds Used:
  • Figure US20180360041A1-20181220-C00217
  • Trial 1: Efficacy Against Septoria tritici on Winter Wheat
  • The trial was conducted under field conditions in Bohl-Iggelheim, Rhineland-palatinate,
  • Germany. Seeds of winter wheat (cv. Riband) were planted and grown under standard conditions with adequate supply of water and nutrients. At growing stage GS 32 (Apr. 14, 2011), a first compound treatment (200 g a.i. per ha) was made with a water volume of 400 L/ha, which was repeated 21 days later at growing stage GS 39. No further fungicide treatments were applied. Infection with fungal pathogens (e.g. Septoria tritici) occurred naturally. The evaluation of the disease incidences for Septoria tritici 20, 33 and 46 days after the last treatment (DAA) are shown in table III. In the last row, the evaluation of the percentage of Qo inhibitor-resistant Septoria tritici isolates with the G143A mutation after the treatments is given.
  • TABLE III
    Percentage of
    Disease (%) G143A mutation
    Concentration 20 33 46 (%) in Septoria
    Treatment (g a.i./ha) DAA DAA DAA tritici isolates
    Compound I-6 200 1 6 36 100
    Pyraclostrobin 200 8 32 93 100
    untreated — 13 47 96 65
  • In this test, the fungal pathogen Septoria tritici has been completely selected towards Qo inhibitor-resistant isolates by each of the treatments with the strobilurin-analogue compounds Pyraclostrobin and Compound I-6. Due to this high resistance level, Pyraclostrobin showed insufficient control level although it has been used at commercial dose levels, whereas Compound I-6 was capable to control the Qo inhibitor-resistant isolates of Septoria tritici with the G143 mutation.
  • Trial 2: Efficacy Against Septoria tritici on Winter Wheat
  • This trial was conducted under field conditions in Limburgerhof, Rhineland-Palatinate, Germany. Seeds of winter wheat (cv. Riband) were planted and grown under standard conditions with adequate supply of water and nutrients. At growing stage GS 33 (Apr. 8, 2011), a first compound treatment (200 g a.i per ha) was made with a water volume of 400 L/ha, which was repeated 26 days later at growing stage GS 39. No further fungicide treatments were applied. Infection with fungal pathogens (e.g. Septoria tritici) occurred naturally. The evaluation of the disease incidences for Septoria tritici 19 and 34 days after the last treatment (DAA) are shown in Table IV. In the last row, the evaluation of the percentage of Qo inhibitor-resistant Septoria tritici isolates with the G143A mutation after the treatments is given.
  • TABLE IV
    Disease (%) Percentage of
    Concentration 19 34 G143A mutation (%)
    Treatment (g a.i./ha) DAA DAA in Septoria tritici isolates
    Compound I-6 200 3 12 99
    Pyraclostrobin 200 5 28 100
    untreated — 10 36 94
  • In this test, about the entire population of the fungal pathogen Septoria tritici has been Qo inhibitor-resistant (as evaluated at the end of the trial). Due to this high resistance level, Pyraclostrobin has shown antifungal activity only slightly above the untreated control although it has been used at commercial dose levels. However Compound I-6 was capable to reduce the infection by Qo inhibitor-resistant Septoria tritici with the G143 mutation significantly.
    • B) Glass House Trials
  • The spray solutions were prepared in several steps:
  • The stock solution was prepared as follows: 1.26 ml of a 1:1 mixture of cyclohexanone and dimethylsulfoxide was added to 8.4 mg of active ingredient. Next, 40.74 ml of a mixture of water, acetone (10%), the emulsifier Wettol (0.1%) and the wetting agent Silwet (0.05%) was added. This stock solution was then further diluted with the described solvent-emulsifier-water mixture to the desired concentrations.
  • Trial 3: Control of Leaf Blotch on Wheat Caused by Caused by Two Septoria tritici Isolates Containing the G143A in the Cytochrome b Gene for their Cytochrome bc1 Complex
  • Wheat plants were grown in pots. These plants were sprayed to run-off with an aqueous suspension, containing the desired concentration of active ingredient. The next day, the treated plants were inoculated with an aqueous suspension of Septoria tritici. After inoculation, the trial plants were covered with a lid and immediately transferred to a chamber with a relative humidity of about 83 to 85% and 19.5 to 20° C. After 4 days the lid was removed. Altogether, the trial plants were cultivated for about 28 days in that greenhouse chamber. The extent of fungal attack on the leaves was then visually assessed as % diseased leaf area.
  • TABLE VII
    Resistant Septoria Resistant Septoria
    tritici isolate 1 tritici isolate 2
    Conc. (G143A mutation) (G143A mutation)
    Treatment (ppm) Disease level (%) Disease level (%)
    I-7 200 3 0
    I-7 100 3 1
    I-7 50 20 5
    I-7 25 80 15
    I-7 12.5 100 90
    I-211 200 1 0
    I-211 100 3 1
    I-211 50 10 5
    I-211 25 60 10
    I-211 12.5 80 30
    I-14 200 3 1
    I-14 100 15 5
    I-14 50 70 15
    I-14 25 80 70
    I-14 12.5 100 90
    I-6 200 1 0
    I-6 100 3 3
    I-6 50 3 3
    I-6 25 10 15
    I-6 12.5 50 20
    I-11 200 1 1
    I-11 100 3 5
    I-11 50 30 30
    I-11 25 90 50
    I-11 12.5 100 70
    Pyraclostrobin 200 30 15
    Pyraclostrobin 100 90 25
    Pyraclostrobin 50 100 40
    Pyraclostrobin 25 100 60
    Pyraclostrobin 12.5 100 60
    Trifloxystrobin 200 90 60
    Trifloxystrobin 100 90 70
    Trifloxystrobin 50 90 70
    Trifloxystrobin 25 100 70
    Trifloxystrobin 12.5 100 80
    • III. MOLECULAR MODELING III.1 Structural Models of Wild-Type and G143A Mutant Binding Site
  • Structural models of the binding site of wild-type and G143A cytochrome bc1 complex were generated based on the crystallographic structure of bovine cytochrome bc1 complex with azoxystrobin bound to the Qo-site (PDB: 1SQB: Esser et al. J Mol Biol 341, 281-302 (2004)).
  • The structure was imported into Schrödinger Maestro (version 9.0, Schrödinger, LLC, New York, N.Y., 2009).
  • Cytochrome b was isolated from the structure of the complex and treated with the Schrödinger Protein Preparation Wizard (Schrödinger Suite 2009 Protein Preparation Wizard; Epik version 2.0, Schrödinger, LLC, New York, N.Y., 2009; Impact version 5.5, Schrödinger, LLC, New York, N.Y., 2009, Prime version 2.1, Schrödinger, LLC, New York, N.Y., 2009).
  • This structure was used as the model for the wild-type binding site without further changes.
  • The model of the G143A mutant was generated by changing a hydrogen in Glycine 143 of the wild-type model into a methyl group, thereby generating S-Alanine, using Schrödinger Maestro. Amino acids in a sphere of 5 Å around the co-crystallized molecule of azoxystrobin were energy-minimized using Schrödinger MacroModel (version 9.7, Schrödinger, LLC, New York, N.Y., 2009).
    • III.2 Molecular Docking
  • Structures of inhibitors were prepared for docking with Schrödinger LigPrep (version 2.3, Schrödinger, LLC, New York, N.Y., 2009) and docked into the structural models using Schrödinger Glide (version 5.5, Schrödinger, LLC, New York, N.Y., 2009).
    • III.3 Graphics of Inhibitors Bound to Cytochrome bc1 Complex
  • Graphical representations of poses from the docking runs were generated using Molecular Operating Environment (MOE; 2010.10; Chemical Computing Group Inc., 1010 Sherbooke St. West, Suite #910, Montreal, QC, Canada, H3A 2R7, 2010) and refined using the GNU Image Manipulation Program (GIMP, version 2.6.8, 2008).
  • As illustrated in FIG. 1 molecular modelling of an artificial Qo inhibitor-resistant cytochrome bc1 complex with the mutation G143A (see below for details) has been carried out. Docking of the commercial storbilurine analogue compound pyraclostrobin shows the steric clash resulting in impaired binding of this active ingredient in the G143A mutant cytochrome bc1 complex. The compounds of the present invention largely avoid this steric clash by either replacing the central phenyl ring of pyraclostrobin with a smaller and/or more flexible two carbon unit which may be suitably substituted or by replacing the well known pharmacophores with the smaller tetrazolinone moiety R4-7.
    • III.4 Number of Van-Der-Waals Clashes Between Inhibitors and Alanine G143A
  • The docked ligands were transferred to the G143A binding site model keeping the coordinates from docking into the wild-type model. Thereby, complexes between the G143A binding site and ligands were formed. Those were used as starting structures for the following energy minimization using Schrödinger MacroModel. During these simulations, only the ligand was allowed to move freely, the protein was considered “frozen”. The poses generated by this procedure were considered as the relaxed state of the inhibitors after introduction of the G143A mutation.
  • Two atoms are considered to be sterically clashing, if the distance between their centers is shorter than 0.9 times the sum of their Van-der-Waals radii. For the atoms pairs relevant for strobilurin interaction with Alanine 143 the respective distances are described in Table V.
  • TABLE V
    vdW-S Clash
    Atom 1 vdW-Radius 1 Atom 2 vdW-Radius 2 um Distance
    C 1.70 C 1.70 3.40 3.06
    C 1.70 N 1.55 3.25 2.93
    C 1.70 O 1.52 3.22 2.90
    C 1.70 H 1.20 2.90 2.61
    H 1.20 N 1.55 2.75 2.48
    H 1.20 O 1.52 2.72 2.45
  • After minimization in the G143A binding site as described above, the number of steric Van-der-Waals clashes with Alanine 143 was counted for each inhibitor. The results are given in the Table VI.
  • TABLE VI
    Compound No. of clashes
    I-5 3
    I-6 3
    Pyrametostrobin 6
    Metominostrobin 6
    Azoxystrobin 7
    Enestroburin 7
    Pyraclostrobin 7
    Dimoxystrobin 7
    Orysastrobin 7
    Pyraoxystrobin 8
    Picoxystrobin 8
    Trifloxystrobin 8
    Kresoxim-Methyl 8
  • It was found that compounds I have a small number of steric Van-der-Waals clashes and also have unexpectedly high activity against Qo inhibitor-resistant fungal strains harboring said G143A mutation in microtiter titer tests as well as in field trials on sites which have a high portion of Qo inhibitor-resistant fungi strains harboring said G143A mutation (see below).

Claims (25)

1. (canceled)
2. A compound of formula (I)
Figure US20180360041A1-20181220-C00218
wherein:
R1, R2 independently of each other are selected from the group consisting of hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-cycloalkyl and C3-C6-cycloalkyl-C1-C4-alkyl, wherein the groups R1 and R2 are cis-oriented, and
wherein the aliphatic moieties of R1 and/or R2 may carry 1, 2, 3 or up to the maximum number of identical or different groups Ra which independently of one another are selected from:
Ra is selected from the group consisting of CN, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-haloalkoxy;
Y is a direct bond or a divalent group selected from the group consisting of —OCH2—, —CH2—, —CH2CH2—, —C(Z)═N—O—CH2—, —CHZ—C(Z)═N—O—CH2—, —O—N═C(Z)—C(Z)═N—O—CH2—, —C(═O)—C(Z)═N—O—CH2— and —C(═N—O—Z)—C(Z)═N—O—CH2—, where the bond depicted on the left side of the divalent group Y is attached to R3, and the bond depicted on the right side is attached to the carbon atom being substituted by R2, and
Z, which may be the same or different to any other Z, is C1-C4-alkyl or C1-C4-haloalkyl;
R3 is selected from pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl or 1,2,4-thia¬diazolyl;
wherein the cyclic groups R3 may carry 1, 2, 3, 4 or up to the maximum possible number of identical or different groups Rb which independently of one another are selected from the group consisting of:
Rb, which may be the same or different to any other Rb, is selected from the group consisting of amino, halogen, hydroxyl, oxo, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C2-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C6-alkoxyimino-C1-C4-alkyl, C2-C6-alkenyloxyimino-C1-C4-alkyl, C2-C6-alkynyloxyimino-C1-C4-alkyl, C1-C4-alkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyloxy, phenyl, naphthyl and a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms selected from the group consisting of N, O and S as ring members; and wherein the aforementioned phenyl and heterocyclyl groups Rb are attached via a direct bond, an oxygen or sulfur atom;
and
two radicals Rb that are bound to adjacent ring member atoms of the cyclic group R3 may form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic cycle, which may be a carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S, and
where the aliphatic or cyclic groups Rb for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rc:
Rc, which may be the same or different to any other Rc, is selected from the group consisting of halogen, hydroxyl, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C8-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C6-alkoxyimino-C1-C4-alkyl, C2-C6-alkenyloxyimino-C1-C4-alkyl, C2-C6-alkynyloxyimino-C1-C4-alkyl, C1-C4-alkoxyimino-C1-C4-alkyl, C1-C6-alkoxyimino-, C2-C6-alkenyloxyimino-, C2-C6-alkynyloxyimino-, C2-C6-haloalkenyloxyimino-, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, phenyl and a 5-membered saturated, partially unsaturated or aromatic heterocyclyl which, in addition to carbon atoms, contains one to three heteroatoms selected from the group consisting of N, O and S as ring members; wherein the aforementioned cyclic groups Rc are attached via a direct bond, an oxygen or sulfur atom and where the aliphatic or cyclic groups Rc for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rd:
Rd, which may be the same or different to any other Rd, is selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-haloalkyl;
or
R3 is —CRA═N—O—RB, wherein
RA is selected from the group consisting of amino, hydroxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C2-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C4-alkoxyimino-C1-C4-alkyl, C1-C4-alkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyloxy, phenyl, phenyl-C1-C4-alkyl, naphthyl and a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members; and wherein the aforementioned cyclic RA are attached via a direct bond, an oxygen or sulfur atom;
RB is selected from the group consisting of C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C1-C4-alkoxyimino-C1-C4-alkyl, C1-C4-alkoxycarbonyl, phenyl, phenyl-C1-C4-alkyl, naphthyl and a 3- to 10-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocyclyl which, in addition to carbon atoms, contains one to four heteroatoms from the group consisting of O, N and S as ring members;
where the aliphatic or cyclic groups RA and/or RB for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Re:
Re, which may be the same or different to any other Re, is selected from the group consisting of halogen, hydroxyl, nitro, CN, carboxyl, C1-C4-alkyl, C2-C4-alkenyl, C2-C8-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
R4 is a monovalent group selected from formulae R4-1 to R4-7
Figure US20180360041A1-20181220-C00219
wherein the jagged line defines the point of attachment, and where
X is a divalent group O or NH,
R5 is selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy and C3-C6-cycloalkyl,
R6 is C1-C4-alkyl or C1-C4-haloalkyl;
and the N-oxides and the agriculturally acceptable salts thereof, except for (2E,3Z)-2-(ethylidene)-5-phenyl-3-pentenoic acid methyl ester (CAS-No. 681026-20-0).
3. The compound of claim 2, wherein R1 is selected from the group consisting of hydrogen, halogen, C1-C4-alkyl, C1-C4-chloroalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl and C1-C4-haloalkoxy-C1-C4-alkyl.
4. The compound of claim 3, wherein R1 is methyl or ethyl.
5. The compound of claim 2, wherein R2 is hydrogen.
6. The compound of claim 2, wherein Y is selected from the group consisting of —OCH2—, —CH2CH2—, —C(CH3)═N—O—CH2—, —O—N═C(CH3)—C(CH3)═N—O—CH2— and —C(═N—O—CH3)—C(CH3)═N—O—CH2—.
7. The compound of claim 1, wherein Rb is phenyl, wherein said phenyl is optionally substituted by 1, 2, 3 or up to the maximum possible number of identical or different groups Rc, which may be the same or different to any other Rc, wherein Rc is selected from the group consisting of halogen, C1-C4-alkyl, C2-C4-alkenyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxyimino-C1-C4-alkyl, phenyl and a 5-membered saturated, partially unsaturated or aromatic heterocyclyl which, in addition to carbon atoms, contains one to three heteroatoms selected from the group consisting of N, O and S as ring members; and wherein the aforementioned heterocyclyl groups Rc are attached via a direct bond, an oxygen or sulfur atom and for their part may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rd.
8. The compound of claim 2, wherein R4 is selected from the group consisting of —C(═NOCH3)—CONHCH3, —C(═NOCH3)—COOCH3, —C(═CHOCH3)COOCH3, —C(═CHOCH3)—CONHCH3, —N(OCH3)—COOCH3, —N(CH3)—COOCH3 and —N(CH2CH3)—COOCH3.
9. The compound of claim 2, wherein R3 is
Figure US20180360041A1-20181220-C00220
wherein # indicates the point of attachment to the linker moiety Y;
wherein the phenyl may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rc, which may be the same or different to any other Rc, is halogen.
10. An agrochemical composition comprising an auxiliary and at least one compound of formula I, as defined in claim 2, an N-oxide or an agriculturally acceptable salt thereof.
11. The composition of claim 10 comprising at least one further active substance.
12. The composition of claim 11, wherein the further active substance is selected from the classes A) to O):
A) Respiration inhibitors
Inhibitors of complex III at Qo site selected from azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, and fenamidone;
inhibitors of complex III at Qi site selected from cyazofamid, amisulbrom, [(3 S,6 S, 7R, 8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate, [(3 S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate, and (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl 2-methylpropanoate;
inhibitors of complex II selected from: benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4′-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1,3-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, and 1,3,5-trimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide;
other respiration inhibitors selected from diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine, binapacryl, dinobuton, dinocap, fluazinam, ferimzone, fentin salts, ametoctradin, and silthiofam;
B) Sterol biosynthesis inhibitors
C14 demethylase inhibitors selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-[rel-(2S; 3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1H-[1,2,4]triazole, 2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1,2,4]triazole-3-thiol, imazalil, pefurazoate, prochloraz, triflumizol, fenarimol, nuarimol, pyrifenox, and triforine;
Delta14-reductase inhibitors selected from aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, and spiroxamine;
Inhibitors of 3-keto reductase selected from fenhexamid;
C) Nucleic acid synthesis inhibitors
phenylamides or acyl amino acid fungicides selected from benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M, ofurace, and oxadixyl;
other nucleic acid synthesis inhibitors selected from hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine, and 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;
D) Inhibitors of cell division and cytoskeleton
benzimidazole and thiophanate tubulin inhibitors selected from benomyl, carbendazim, fuberidazole, thiabendazole, and thiophanate-methyl;
triazolopyrimidines selected from 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine;
other cell division inhibitors selected from diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, and pyriofenone;
E) Inhibitors of amino acid and protein synthesis
methionine synthesis inhibitors selected from cyprodinil, mepanipyrim, and pyrimethanil;
protein synthesis inhibitors selected from blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, and validamycin A;
F) Signal transduction inhibitors
MAP/histidine kinase inhibitors selected from fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, and fludioxonil;
G protein inhibitors selected from quinoxyfen;
G) Lipid and membrane synthesis inhibitors
Phospholipid biosynthesis inhibitors selected from edifenphos, iprobenfos, pyrazophos, and isoprothiolane;
lipid peroxidation inhibitors selected from dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, and etridiazole;
phospholipid biosynthesis and cell wall deposition inhibitors selected from: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl), and carbamic acid-(4-fluorophenyl) ester;
compounds affecting cell membrane permeability and fatty acids selected from propamocarb and propamocarb-hydrochlorid;
fatty acid amide hydrolase inhibitor selected from 1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone;
H) Inhibitors with Multi-site Action
inorganic active substances selected from Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
thio- and dithiocarbamates selected from ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, and ziram;
organochlorine compounds selected from anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, and N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methyl-benzenesulfonamide;
guanidines and other inhibitors with multi-site action selected from guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, and 2,6-dimethyl-1H,5H[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetraone;
I) Cell wall synthesis inhibitors
inhibitors of glucan synthesis selected from: validamycin and polyoxin B;
melanin synthesis inhibitors selected from pyroquilon, tricyclazole, carpropamid, dicyclomet, and fenoxanil;
J) Plant defence inducers selected from:
acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum, and phosphorous acid and its salts;
K) Active substances with unknown mode of actions selected from:
bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxathiapiprolin, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoromethoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N′-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N′-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N′-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N′-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole, and 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxyphenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
L) Antifungal biocontrol agents and plant bioactivators selected from:
Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus pumilus, Bacillus subtilis, Bacillus subtilis var. amyloliquefaciens FZB24, Candida oleophila I-82, Candida saitoana, Chitosan, Clonostachys rosea f. catenulata, Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Fusarium oxysporum, Metschnikowia fructicola, Microdochium dimerum, Phlebiopsis gigantea, Pseudozyma flocculosa, Pythium oligandrum DV74, Reynoutria sachlinensis, Talaromyces flavus V117b, Trichoderma asperellum SKT-1, T. atroviride LC52, T. harzianum T-22, T. harzianum TH 35, T. harzianum T-39, T. harzianum and T. viride, T. harzianum ICC012 and T. viride ICC080, T. polysporum and T. harzianum, T. stromaticum, T. virens GL-21, T. viride, T. viride TV1, and Ulocladium oudemansii HRU3;
M) Growth regulators selected from:
abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat chloride, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid, and trinexapac-ethyl and uniconazole;
N) Herbicides
acetamides selected from acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, and thenylchlor;
amino acid derivatives selected from bilanafos, glyphosate, glufosinate, and sulfosate;
aryloxyphenoxypropionates selected from clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, and quizalofop-P-tefuryl;
Bipyridyls selected from diquat and paraquat;
(thio)carbamates selected from asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam, esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, and triallate;
cyclohexanediones selected from butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, and tralkoxydim;
dinitroanilines selected from benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, and trifluralin;
diphenyl ethers selected from acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, and oxyfluorfen;
hydroxybenzonitriles selected from bomoxynil, dichlobenil, and ioxynil;
imidazolinones selected from imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, and imazethapyr;
phenoxy acetic acids selected from clomeprop, 2,4-dichlorophenoxyacetic acid, 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, and Mecoprop;
pyrazines selected from chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, and pyridate;
pyridines selected from aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, and thiazopyr;
sulfonyl ureas selected from amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, and 1-((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea;
triazines selected from ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, and triaziflam;
ureas selected from chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, methabenzthiazuron, and tebuthiuron;
other acetolactate synthase inhibitors selected from: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, and pyroxsulam;
other herbicides selected from amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester;
O) Insecticides
organo(thio)phosphates selected from acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
carbamates selected from: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, and triazamate;
pyrethroids selected from: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, and dimefluthrin;
insect growth regulators selected from a) chitin synthesis inhibitors selected from benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, and clofentazine; b) ecdysone antagonists selected from halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, and fenoxycarb; and d) lipid biosynthesis inhibitors selected from spirodiclofen, spiromesifen, and spirotetramat;
nicotinic receptor agonists/antagonists compounds selected from clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, and 1-(2-chloro-thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1,3,5]triazinane;
GABA antagonist compounds selected from endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, and 5-amino-1-(2,6-dichloro-4-methylphenyl)-4-sulfinamoyl-1H-pyrazole-3-carbothioic acid amide;
macrocyclic lactone insecticides selected from abamectin, emamectin, milbemectin, lepimectin, spinosad, and spinetoram;
mitochondrial electron transport inhibitor I acaricides selected from fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, and flufenerim;
METI II and III compounds selected from acequinocyl, fluacyprim, and hydramethylnon;
Uncouplers selected from chlorfenapyr;
oxidative phosphorylation inhibitors selected from cyhexatin, diafenthiuron, fenbutatin oxide, and propargite;
moulting disruptor compound selected from cryomazine;
mixed function oxidase inhibitor selected from piperonyl butoxide;
sodium channel blockers selected from indoxacarb and metaflumizone;
other insecticides selected from benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr, cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, and pyrifluquinazon.
13. The composition of claim 10, wherein R1 in the compound of formula I is selected from the group consisting of hydrogen, C1-C4-alkyl, C1-C4-chloroalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl and C1-C4-haloalkoxy-C1-C4-alkyl.
14. The composition of claim 10, wherein R1 in the compound of formula I is methyl or ethyl.
15. The composition of claim 10, wherein R2 in the compound of formula I is hydrogen.
16. A method for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, wherein the mutation is G143A, comprising applying a pesticidally effective amount of compound of formula (I) according to claim 2.
17. The method of claim 16, wherein the phytopathogenic fungi are selected from the group consisting of Alternaria alternata, Blumeria graminis, Pyricularia oryzae, Septoria tritici, Mycosphaerella fijiensis, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis and Plasmopara viticola.
18. The method of claim 17, wherein the phytopathogenic fungus is Septoria tritici.
19. The method of claim 16, comprising:
treating the phytopathogenic fungi or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi with an effective amount of at least one compound of formula I, or a composition comprising it thereof.
20. The method of claim 19, comprising:
a) identifying the phytopathogenic fungi, or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi, and
treating said fungi or the materials, plants, the soil or seeds with an effective amount of at least one compound of formula I, or a composition comprising it thereof.
21: Agrochemical compositions wherein said compositions comprise an auxiliary and at least one compound of formula (I):
wherein:
R1 and R2 together with the two carbon atoms linking them form a phenyl ring and
R4 is 4-methyl-1,4-dihydro-tetrazol-5-one-1 yl, and
wherein the abovementioned phenyl ring may carry 1, 2, 3 or up to the maximum number of identical or different groups Ra which independently of one another are selected from:
Ra CN, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and C1-C4-haloalkoxy;
Y is a direct bond or a divalent group selected from —CH2—, —CH2CH2—, —C(Z)═N—O—CH2—, —CHZ—C(Z)═N—O—CH2—, —O—N═C(Z)—C(Z)═N—O—CH2—, —C(═O)—C(Z)═N—O—CH2— and —C(═N—O—Z)—C(Z)═N—O—CH2—,
where the bond depicted on the left side of the divalent group Y is attached to R3, and the bond depicted on the right side is attached to the carbon atom being substituted by R2, and
Z which may be the same or different to any other Z, is hydrogen, C1-C4-alkyl or C1-C4-haloalkyl;
R3 is
Figure US20180360041A1-20181220-C00221
wherein # indicates the point of attachment to the linker moiety Y;
wherein the phenyl may carry 1, 2, 3 or up to the maximum possible number of identical or different groups Rc, which may be the same or different to any other Rc, is halogen
or an N-oxide or an agriculturally acceptable salt thereof,
and at least one further active substance selected from the classes A) and B):
A) Respiration inhibitors
Inhibitors of complex III at Qo site: coumethoxystrobin, coumoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide;
inhibitors of complex II: benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4′-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1,3-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1,3,5-trimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide;
other respiration inhibitors: diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts; ametoctradin; and silthiofam; and
B) Sterol biosynthesis inhibitors (SBI fungicides)
C14 demethylase inhibitors: prothioconazole, simeconazole, 1-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1H-[1,2,4]triazole, 2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1,2,4]triazole-3-thiol.
21: The agrochemical compositions of claim 20, wherein the further active substance is pyraclostrobin.
22: The agrochemical compositions of claim 20, wherein the further active substance is selected from benzovindiflupyr, bixafen, boscalid, fluopyram, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, sedaxane; ametoctradin and fluazinam.
23: The agrochemical compositions of claim 8, wherein the further active substance is prothioconazole.
24: The agrochemical compositions of claim 20, which comprise one compound of formula I as component 1) and one further active substance as component 2) and wherein the weight ratio of component 1) and component 2) is in the range of 1:20 to 20:1.
US16/112,176 2011-12-21 2018-08-24 Use of Strobilurin Type Compounds for Combating Phytopathogenic Fungi Resistant to QO Inhibitors Abandoned US20180360041A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/112,176 US20180360041A1 (en) 2011-12-21 2018-08-24 Use of Strobilurin Type Compounds for Combating Phytopathogenic Fungi Resistant to QO Inhibitors

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
EP11195032 2011-12-21
EP11195032.5 2011-12-21
EP12190109.4 2012-10-26
EP12190109 2012-10-26
PCT/EP2012/074586 WO2013092224A1 (en) 2011-12-21 2012-12-06 Use of strobilurin type compounds for combating phytopathogenic fungi resistant to qo inhibitors
US201414364532A 2014-06-11 2014-06-11
US15/054,828 US10080365B2 (en) 2011-12-21 2016-02-26 Use of strobilurin type compounds for combating phytopathogenic fungi resistant to Qo inhibitors
US16/112,176 US20180360041A1 (en) 2011-12-21 2018-08-24 Use of Strobilurin Type Compounds for Combating Phytopathogenic Fungi Resistant to QO Inhibitors

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US15/054,828 Continuation US10080365B2 (en) 2011-12-21 2016-02-26 Use of strobilurin type compounds for combating phytopathogenic fungi resistant to Qo inhibitors

Publications (1)

Publication Number Publication Date
US20180360041A1 true US20180360041A1 (en) 2018-12-20

Family

ID=47290995

Family Applications (3)

Application Number Title Priority Date Filing Date
US14/364,532 Active US9271501B2 (en) 2011-12-21 2012-12-06 Use of strobilurin type compounds for combating phytopathogenic fungi resistant to QO inhibitors
US15/054,828 Active US10080365B2 (en) 2011-12-21 2016-02-26 Use of strobilurin type compounds for combating phytopathogenic fungi resistant to Qo inhibitors
US16/112,176 Abandoned US20180360041A1 (en) 2011-12-21 2018-08-24 Use of Strobilurin Type Compounds for Combating Phytopathogenic Fungi Resistant to QO Inhibitors

Family Applications Before (2)

Application Number Title Priority Date Filing Date
US14/364,532 Active US9271501B2 (en) 2011-12-21 2012-12-06 Use of strobilurin type compounds for combating phytopathogenic fungi resistant to QO inhibitors
US15/054,828 Active US10080365B2 (en) 2011-12-21 2016-02-26 Use of strobilurin type compounds for combating phytopathogenic fungi resistant to Qo inhibitors

Country Status (22)

Country Link
US (3) US9271501B2 (en)
EP (1) EP2793579B3 (en)
JP (2) JP6189324B2 (en)
KR (1) KR102066829B1 (en)
CN (1) CN104010502B (en)
BR (1) BR112014015535A8 (en)
CA (1) CA2856954C (en)
CL (1) CL2014001421A1 (en)
CO (1) CO7000781A2 (en)
CR (1) CR20140247A (en)
DK (1) DK2793579T6 (en)
EA (1) EA024331B1 (en)
ES (1) ES2590466T7 (en)
HU (1) HUE030004T2 (en)
IL (1) IL232796A (en)
IN (1) IN2014CN04984A (en)
MX (1) MX2014006517A (en)
PE (1) PE20141431A1 (en)
PL (1) PL2793579T6 (en)
PT (1) PT2793579T (en)
WO (1) WO2013092224A1 (en)
ZA (1) ZA201404495B (en)

Families Citing this family (289)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HU231053B1 (en) * 2011-09-08 2020-03-30 Szegedi Tudományegyetem Copper-resistant, fengycin hyperproducing bacillus mojavensis strain for protection against plant pests, its use and compounds containing the same
US9271501B2 (en) 2011-12-21 2016-03-01 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi resistant to QO inhibitors
JP6075182B2 (en) 2012-04-27 2017-02-08 住友化学株式会社 Tetrazolinone compounds and uses thereof
JP6107377B2 (en) 2012-04-27 2017-04-05 住友化学株式会社 Tetrazolinone compounds and uses thereof
US9386773B2 (en) * 2012-05-30 2016-07-12 Bayer Cropscience Ag Compositions comprising a biological control agent and a fungicide from the group consisting of inhibitors of the respiratory chain at complex I or II
JP6142753B2 (en) 2012-09-28 2017-06-07 住友化学株式会社 Tetrazolinone compounds and uses thereof
JP6142752B2 (en) 2012-09-28 2017-06-07 住友化学株式会社 Tetrazolinone compounds and uses thereof
CN104822666B (en) 2012-11-29 2016-09-21 住友化学株式会社 Terazololine-one compound and application thereof
US9560850B2 (en) 2012-12-27 2017-02-07 Sumitomo Chemical Company, Limited Tetrazolinone compound and use thereof
WO2014104382A1 (en) * 2012-12-27 2014-07-03 住友化学株式会社 Tetrazolinone compound and applications thereof
WO2014104268A1 (en) * 2012-12-27 2014-07-03 住友化学株式会社 Tetrazolinone compound and applications thereof
CN105339359B (en) 2013-04-26 2018-02-16 住友化学株式会社 Terazololine-one compound and application thereof
WO2014202421A1 (en) * 2013-06-18 2014-12-24 Basf Se Fungicidal mixtures i comprising strobilurin-type fungicides
EP2815649A1 (en) * 2013-06-18 2014-12-24 Basf Se Fungicidal mixtures II comprising strobilurin-type fungicides
WO2015005355A1 (en) * 2013-07-10 2015-01-15 Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 Synergistic plant disease-controlling composition comprising picolinic acid derivative
EP3020715B1 (en) * 2013-07-12 2021-06-16 Sumitomo Chemical Company Limited Tetrazolinone compound and use thereof
CA2918709C (en) 2013-07-22 2021-07-13 Sumitomo Chemical Company, Limited Plant fungal disease control composition and its use
SI3025584T1 (en) * 2013-07-22 2018-04-30 Sumitomo Chemical Company, Limited Plant disease control composition and its use
AU2014294145B2 (en) 2013-07-22 2017-06-01 Sumitomo Chemical Company, Limited Plant disease control composition and application for same
WO2015016335A1 (en) * 2013-07-31 2015-02-05 住友化学株式会社 Tetrazolinone compound and use thereof
CN105492432B (en) * 2013-07-31 2019-06-14 住友化学株式会社 Terazololine-one compound and application thereof
JP6428618B2 (en) * 2013-07-31 2018-11-28 住友化学株式会社 Tetrazolinone compounds and uses thereof
CN104336079A (en) * 2013-08-01 2015-02-11 陕西美邦农药有限公司 A compound sterilization composition containing oxathiapiprolin
CN103430964A (en) * 2013-08-14 2013-12-11 南京农业大学 Composition containing bacillus subtilis and chloropiperidine ester
BR112016004003B1 (en) * 2013-08-29 2021-07-06 Sumitomo Chemical Company, Limited tetrazolinone compound and its use
WO2015046480A1 (en) * 2013-09-25 2015-04-02 住友化学株式会社 Tetrazolinone compound and use thereof
CN105658630A (en) * 2013-10-25 2016-06-08 住友化学株式会社 Tetrazolinone compound and use thereof
JP6432517B2 (en) * 2013-10-28 2018-12-05 住友化学株式会社 Tetrazolinone compounds and uses thereof
CN103642700B (en) * 2013-12-04 2015-09-02 青海省农林科学院 One strain aureobasidium pullulans and application thereof
CN105873909A (en) 2013-12-12 2016-08-17 巴斯夫欧洲公司 Substituted [1,2,4]triazole and imidazole compounds
CN103719125A (en) * 2013-12-25 2014-04-16 江苏龙灯化学有限公司 Bactericide composition and application thereof
UA117521C2 (en) 2014-03-26 2018-08-10 Басф Се Substituted [1,2,4]triazole and imidazole compounds as fungicides
EP3124485B1 (en) 2014-03-28 2018-11-28 Sumitomo Chemical Company Limited Tetrazolinone compounds for controlling pests
US9826741B2 (en) 2014-03-28 2017-11-28 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
CN106132938B (en) * 2014-03-28 2019-05-17 住友化学株式会社 Terazololine-one compound and its application
AU2015261166A1 (en) 2014-05-13 2016-12-01 Basf Se Substituted [1,2,4]triazole and imidazole compounds as fungicides
EP2952507A1 (en) 2014-06-06 2015-12-09 Basf Se Substituted [1,2,4]triazole compounds
EP2952512A1 (en) 2014-06-06 2015-12-09 Basf Se Substituted [1,2,4]triazole compounds
EP3756464A1 (en) 2014-06-06 2020-12-30 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP2952506A1 (en) 2014-06-06 2015-12-09 Basf Se Substituted [1,2,4]triazole and imidazole compounds
AR100743A1 (en) 2014-06-06 2016-10-26 Basf Se COMPOUNDS OF [1,2,4] SUBSTITUTED TRIAZOL
WO2015197458A1 (en) * 2014-06-27 2015-12-30 Basf Se Substituted 1-[2-[[[2-alkoxyimino-alkenylidene]amino]oxymethyl]phenyl]-4-methyl-tetrazol-5-one compounds as phytopathogenic fungicides
CN104839165A (en) * 2014-09-09 2015-08-19 陕西美邦农药有限公司 Benzovindiflupyr sterilization composition
EP3204390B1 (en) 2014-10-06 2019-06-05 Basf Se Substituted pyrimidinium compounds for combating animal pests
KR20170070035A (en) * 2014-10-10 2017-06-21 바스프 에스이 Stereoselective process to obtain (z)-5-cyclyloxy-2-[(e)-methoxyimino]-3-methyl-pent-3-enic acid methyl amides using e,z-isomer mixture of and intermediates thereof
RU2707051C2 (en) 2014-10-24 2019-11-21 Басф Се Non-ampholytic, quaternizable and water-soluble polymers for modifying surface charge of solid particles
US20180368404A1 (en) 2014-11-06 2018-12-27 Basf Se 3-pyridyl heterobicyclic compound for controlling invertebrate pests
WO2016071167A1 (en) 2014-11-07 2016-05-12 Basf Se Pesticidal mixtures
CR20170210A (en) * 2014-11-26 2017-09-25 Bayer Cropscience Lp METHODS AND COMPOSITIONS TO CONTROL PATHOGENIC FUNGI IN CROP PLANTS
WO2016088747A1 (en) * 2014-12-01 2016-06-09 日産化学工業株式会社 Hydrazone derivative and pest control agent
CN104585178A (en) * 2014-12-24 2015-05-06 江西中迅农化有限公司 Synergetic acaricidal composition containing cyenopyrafen and spirodiclofen
BR112017014651B1 (en) 2015-01-13 2021-05-04 Sumitomo Chemical Company, Limited carbamate compound, its use, agent and method to control plant diseases
WO2016124769A1 (en) 2015-02-06 2016-08-11 Basf Se Pyrazole compounds as nitrification inhibitors
WO2016128240A1 (en) 2015-02-11 2016-08-18 Basf Se Pesticidal mixture comprising a pyrazole compound and two fungicides
BR112017015061B1 (en) 2015-02-11 2022-09-27 Basf Se PESTICIDE MIXTURE COMPRISING AN ACTIVE COMPOUND OF FORMULA IA AND BROFLANILIDE
US11064696B2 (en) 2015-04-07 2021-07-20 Basf Agrochemical Products B.V. Use of an insecticidal carboxamide compound against pests on cultivated plants
CN104770368B (en) * 2015-04-16 2017-03-15 山东省果树研究所 Bactericidal composition and its application containing SYP-3375 and octyl trichlamide
CN104798786B (en) * 2015-05-07 2016-07-06 深圳诺普信农化股份有限公司 A kind of bactericidal composition containing benzo alkene fluorine bacterium azoles and application thereof
RU2017143177A (en) 2015-05-12 2019-06-13 Басф Се Thioether compounds as inhibitors of nitrification
WO2016198611A1 (en) 2015-06-11 2016-12-15 Basf Se N-(thio)acylimino heterocyclic compounds
WO2016198613A1 (en) 2015-06-11 2016-12-15 Basf Se N-(thio)acylimino compounds
WO2017016883A1 (en) 2015-07-24 2017-02-02 Basf Se Process for preparation of cyclopentene compounds
KR20180059891A (en) 2015-10-02 2018-06-05 바스프 에스이 An imino compound having a 2-chloropyrimidin-5-yl substituent as an antipruritic agent
CN108137533A (en) 2015-10-05 2018-06-08 巴斯夫欧洲公司 Prevent the pyridine compounds of plant pathogenic fungi
UY36964A (en) 2015-10-27 2017-05-31 Bayer Cropscience Ag COMBINATIONS OF ACTIVE PRINCIPLES THAT INCLUDE A DERIVATIVE OF (UNCLE) CARBOXAMIDE AND A FUNGUITED COMPOUND
EP3371177A1 (en) 2015-11-02 2018-09-12 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP3165094A1 (en) 2015-11-03 2017-05-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018008288A2 (en) 2015-11-04 2018-10-30 Basf Se use of formula compounds, formula compounds, mixture, agrochemical composition and method for combating fungi
EP3165093A1 (en) 2015-11-05 2017-05-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP3167716A1 (en) 2015-11-10 2017-05-17 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP3373732A1 (en) 2015-11-13 2018-09-19 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018009579A2 (en) 2015-11-13 2018-11-06 Basf Se compound of formula i, mixture, agrochemical composition, compound use and fungal control method
CA3003949A1 (en) 2015-11-19 2017-05-26 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US10499644B2 (en) 2015-11-19 2019-12-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US11076600B2 (en) 2015-11-30 2021-08-03 Basf Se Mixtures of cis-jasmone and bacillus amyloliquefaciens
CN108290840A (en) 2015-12-01 2018-07-17 巴斯夫欧洲公司 Pyridine compounds as fungicide
BR112018010140A8 (en) 2015-12-01 2019-02-26 Basf Se compounds of formula, composition, use of a compound of formula, method for combating phytopathogenic fungi and seed
EP3205208A1 (en) 2016-02-09 2017-08-16 Basf Se Mixtures and compositions comprising paenibacillus strains or fusaricidins and chemical pesticides
US20190077809A1 (en) 2016-03-09 2019-03-14 Basf Se Spirocyclic Derivatives
BR112018017034A2 (en) 2016-03-10 2018-12-26 Basf Se mixtures and their use, agrochemical composition, method of controlling phytopathogenic weeds and plant propagation material
BR112018068042A2 (en) 2016-03-11 2019-01-08 Basf Se methods for controlling plant pests, plant propagating material and use of one or more compounds of formula i
US11241012B2 (en) 2016-03-16 2022-02-08 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on soybean
EP3429359A1 (en) * 2016-03-16 2019-01-23 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on cereals as a seed treatment
WO2017157923A1 (en) * 2016-03-16 2017-09-21 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on agricultural plants
EP3429358A1 (en) 2016-03-16 2019-01-23 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on fruits
EP3429357A1 (en) 2016-03-16 2019-01-23 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on cereals
WO2017167832A1 (en) 2016-04-01 2017-10-05 Basf Se Bicyclic compounds
US10986839B2 (en) 2016-04-11 2021-04-27 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017198588A1 (en) 2016-05-18 2017-11-23 Basf Se Capsules comprising benzylpropargylethers for use as nitrification inhibitors
EP3245872A1 (en) 2016-05-20 2017-11-22 BASF Agro B.V. Pesticidal compositions
WO2017207368A1 (en) 2016-06-02 2017-12-07 BASF Agro B.V. Fungicidal compositions
CN106305741A (en) * 2016-08-15 2017-01-11 青岛瀚生生物科技股份有限公司 Agricultural compound bactericide and application thereof
WO2018050421A1 (en) 2016-09-13 2018-03-22 Basf Se Fungicidal mixtures i comprising quinoline fungicides
WO2018054721A1 (en) 2016-09-26 2018-03-29 Basf Se Pyridine compounds for controlling phytopathogenic harmful fungi
WO2018054711A1 (en) 2016-09-26 2018-03-29 Basf Se Pyridine compounds for controlling phytopathogenic harmful fungi
WO2018054723A1 (en) 2016-09-26 2018-03-29 Basf Se Pyridine compounds for controlling phytopathogenic harmful fungi
WO2018065182A1 (en) 2016-10-04 2018-04-12 Basf Se Reduced quinoline compounds as antifuni agents
WO2018073110A1 (en) 2016-10-20 2018-04-26 Basf Se Quinoline compounds as fungicides
CN110291072A (en) 2016-12-16 2019-09-27 巴斯夫欧洲公司 Agricultural chemical compound
BR112019011293A2 (en) 2016-12-19 2019-10-08 Basf Se compounds of formula I, intermediates, agrochemical composition, use and method for combating phytopathogenic harmful fungi
EP3339297A1 (en) 2016-12-20 2018-06-27 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP3338552A1 (en) 2016-12-21 2018-06-27 Basf Se Use of a tetrazolinone fungicide on transgenic plants
BR112019014061A2 (en) 2017-01-23 2020-02-04 Basf Se compounds of formula i, intermediates b, intermediates c, intermediates ii and intermediates d, composition, use, method to combat phytopathogenic fungi, seed and process for the synthesis of the compounds of formula i
TWI760428B (en) 2017-01-26 2022-04-11 日商三井化學Agro股份有限公司 Pyridone compound and germicide for agriculture and horticulture using the same as active ingredient
WO2018149754A1 (en) 2017-02-16 2018-08-23 Basf Se Pyridine compounds
BR112019015338B1 (en) 2017-02-21 2023-03-14 Basf Se COMPOUNDS OF FORMULA I, AGROCHEMICAL COMPOSITION, COATED SEED, USE OF THE COMPOUNDS AND METHOD TO COMBAT HARMFUL PHYTOPATHOGENIC FUNGI
WO2018153707A1 (en) 2017-02-22 2018-08-30 Basf Se Crystalline forms of a strobilurin type compound for combating phytopathogenic fungi
WO2018162312A1 (en) 2017-03-10 2018-09-13 Basf Se Spirocyclic derivatives
WO2018166855A1 (en) 2017-03-16 2018-09-20 Basf Se Heterobicyclic substituted dihydroisoxazoles
ES2950451T3 (en) 2017-03-28 2023-10-10 Basf Se Pesticide compounds
MX2019011785A (en) 2017-03-31 2019-11-18 Basf Se Process for preparing chiral 2,3-dihydrothiazolo[3,2-a]pyrimidin- 4-ium compounds.
EP3606914A1 (en) 2017-04-06 2020-02-12 Basf Se Pyridine compounds
CA3056347A1 (en) 2017-04-07 2018-10-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018190351A1 (en) 2017-04-10 2018-10-18 三井化学アグロ株式会社 Pyridone compound, and agricultural and horticultural fungicide having this as active component
US11147272B2 (en) 2017-04-10 2021-10-19 Mitsui Chemicals Argro, Inc. Pyridone compounds and agricultural and horticultural fungicides comprising the same as active ingredients
CN110234627B (en) 2017-04-11 2023-09-01 三井化学植保株式会社 Pyridone compound and agricultural/horticultural bactericide containing pyridone compound as active ingredient
WO2018188962A1 (en) 2017-04-11 2018-10-18 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018192793A1 (en) 2017-04-20 2018-10-25 Basf Se Substituted rhodanine derivatives
MX2019012468A (en) 2017-04-20 2019-12-11 Pi Industries Ltd Novel phenylamine compounds.
JP2020517672A (en) 2017-04-26 2020-06-18 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Substituted succinimide derivatives as pesticides
EP3618629A1 (en) 2017-05-02 2020-03-11 Basf Se Fungicidal mixture comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles
WO2018202491A1 (en) 2017-05-04 2018-11-08 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
CN110621669A (en) 2017-05-04 2019-12-27 巴斯夫欧洲公司 Substituted 5-haloalkyl-5-hydroxyisoxazoles for controlling phytopathogenic fungi
WO2018202737A1 (en) 2017-05-05 2018-11-08 Basf Se Fungicidal mixtures comprising triazole compounds
JP2020519607A (en) 2017-05-10 2020-07-02 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Bicyclic pesticide compounds
WO2018210659A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
WO2018210661A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
WO2018210658A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
WO2018210660A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
EP3625215B1 (en) 2017-05-18 2023-09-13 PI Industries Ltd Formimidamidine compounds useful against phytopathogenic microorganisms
US11737463B2 (en) 2017-05-30 2023-08-29 Basf Se Pyridine and pyrazine compounds
WO2018219797A1 (en) 2017-06-02 2018-12-06 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018224455A1 (en) 2017-06-07 2018-12-13 Basf Se Substituted cyclopropyl derivatives
WO2018225829A1 (en) 2017-06-08 2018-12-13 三井化学アグロ株式会社 Pyridone compound and agricultural and horticultural fungicide
CN110770235A (en) 2017-06-16 2020-02-07 巴斯夫欧洲公司 Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2018234202A1 (en) 2017-06-19 2018-12-27 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests
US20200190043A1 (en) 2017-06-19 2020-06-18 Basf Se 2-[[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]aryloxy](thio)acetamides for combating phytopathogenic fungi
WO2018234488A1 (en) 2017-06-23 2018-12-27 Basf Se Substituted cyclopropyl derivatives
WO2019002158A1 (en) 2017-06-30 2019-01-03 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
EP3427587A1 (en) 2017-07-10 2019-01-16 Basf Se Pesticidal mixtures
WO2019025250A1 (en) 2017-08-04 2019-02-07 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
US10743535B2 (en) 2017-08-18 2020-08-18 H&K Solutions Llc Insecticide for flight-capable pests
WO2019038042A1 (en) 2017-08-21 2019-02-28 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
EP3915379A1 (en) 2017-08-29 2021-12-01 Basf Se Pesticidal mixtures
WO2019042932A1 (en) 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
EP3453706A1 (en) 2017-09-08 2019-03-13 Basf Se Pesticidal imidazole compounds
US11076596B2 (en) 2017-09-18 2021-08-03 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019057660A1 (en) 2017-09-25 2019-03-28 Basf Se Indole and azaindole compounds with substituted 6-membered aryl and heteroaryl rings as agrochemical fungicides
US11399543B2 (en) 2017-10-13 2022-08-02 Basf Se Substituted 1,2,3,5-tetrahydroimidazo[1,2-a]pyrimidiniumolates for combating animal pests
EP3713936B1 (en) 2017-11-23 2021-10-20 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019115511A1 (en) 2017-12-14 2019-06-20 Basf Se Fungicidal mixture comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles
WO2019115343A1 (en) 2017-12-15 2019-06-20 Basf Se Fungicidal mixture comprising substituted pyridines
WO2019125294A1 (en) * 2017-12-19 2019-06-27 Funck Jensen Dan Bca control of stb
WO2019121143A1 (en) 2017-12-20 2019-06-27 Basf Se Substituted cyclopropyl derivatives
EP3728204A1 (en) 2017-12-20 2020-10-28 PI Industries Ltd. Fluoralkenyl compounds, process for preparation and use thereof
CN111491925B (en) 2017-12-21 2023-12-29 巴斯夫欧洲公司 Pesticidal compounds
UA127764C2 (en) 2018-01-09 2023-12-27 Басф Се Silylethynyl hetaryl compounds as nitrification inhibitors
WO2019137995A1 (en) 2018-01-11 2019-07-18 Basf Se Novel pyridazine compounds for controlling invertebrate pests
EP3746439A2 (en) 2018-01-30 2020-12-09 PI Industries Ltd. Oxadiazoles for use in controlling phytopathogenic fungi
WO2019150311A1 (en) 2018-02-02 2019-08-08 Pi Industries Ltd. 1-3 dithiol compounds and their use for the protection of crops from phytopathogenic microorganisms
WO2019154665A1 (en) 2018-02-07 2019-08-15 Basf Se New pyridine carboxamides
US20200354321A1 (en) 2018-02-07 2020-11-12 Basf Se New pyridine carboxamides
EP3530118A1 (en) 2018-02-26 2019-08-28 Basf Se Fungicidal mixtures
EP3530116A1 (en) 2018-02-27 2019-08-28 Basf Se Fungicidal mixtures comprising xemium
KR20200128052A (en) 2018-02-28 2020-11-11 바스프 에스이 Use of alkoxypyrazoles as nitrification inhibitors
CA3089381A1 (en) 2018-02-28 2019-09-06 Basf Se Use of pyrazole propargyl ethers as nitrification inhibitors
CA3093781A1 (en) 2018-02-28 2019-09-06 Basf Se Use of n-functionalized alkoxy pyrazole compounds as nitrification inhibitors
BR112020015467A2 (en) 2018-02-28 2020-12-08 Basf Se FUNGICIDAL MIXTURES, FUNGICIDAL COMPOSITION, METHODS TO CONTROL PHYTOPATOGENIC FUNGI, TO IMPROVE PLANT HEALTH AND TO PROTECT PLANT PROPAGATION MATERIAL AGAINST PHYTOPHOGENIC FUNGI AND PLANT PROPAGATION MATERIAL
CN111801014B (en) 2018-03-01 2022-05-27 巴斯夫农业公司 Fungicidal compositions of cloroxen
EP3533333A1 (en) 2018-03-02 2019-09-04 Basf Se Fungicidal mixtures comprising pydiflumetofen
EP3533331A1 (en) 2018-03-02 2019-09-04 Basf Se Fungicidal mixtures comprising pydiflumetofen
EP3536150A1 (en) 2018-03-06 2019-09-11 Basf Se Fungicidal mixtures comprising fluxapyroxad
BR112020018403A2 (en) 2018-03-09 2020-12-22 Pi Industries Ltd. HETEROCYCLIC COMPOUNDS WITH FUNGICIDES
WO2019175712A1 (en) 2018-03-14 2019-09-19 Basf Corporation New uses for catechol molecules as inhibitors to glutathione s-transferase metabolic pathways
WO2019175713A1 (en) 2018-03-14 2019-09-19 Basf Corporation New catechol molecules and their use as inhibitors to p450 related metabolic pathways
WO2019185413A1 (en) 2018-03-27 2019-10-03 Basf Se Pesticidal substituted cyclopropyl derivatives
WO2019202459A1 (en) 2018-04-16 2019-10-24 Pi Industries Ltd. Use of 4-substituted phenylamidine compounds for controlling disease rust diseases in plants
WO2019219464A1 (en) 2018-05-15 2019-11-21 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
CN112423590B (en) 2018-05-15 2022-07-08 巴斯夫欧洲公司 Mixtures and use comprising benzpyrimoxan and oxazosulfyl and methods for their application
WO2019224092A1 (en) 2018-05-22 2019-11-28 Basf Se Pesticidally active c15-derivatives of ginkgolides
WO2020002472A1 (en) 2018-06-28 2020-01-02 Basf Se Use of alkynylthiophenes as nitrification inhibitors
DK3826982T3 (en) 2018-07-23 2024-01-22 Basf Se USE OF A SUBSTITUTED THIAZOLIDE COMPOUND AS A NITRIFICATION INHIBITOR
CN112424148B (en) 2018-07-23 2023-08-11 巴斯夫欧洲公司 Use of substituted 2-thiazolines as nitrification inhibitors
US20210267202A1 (en) 2018-07-25 2021-09-02 Mitsui Chemicals Agro, Inc. Pyridone compounds and agricultural and horticultural fungicides containing the same as active ingredients
WO2020035826A1 (en) 2018-08-17 2020-02-20 Pi Industries Ltd. 1,2-dithiolone compounds and use thereof
EP3613736A1 (en) 2018-08-22 2020-02-26 Basf Se Substituted glutarimide derivatives
CN113015433A (en) * 2018-09-14 2021-06-22 Fmc公司 Fungicidal halomethyl ketones and hydrates
EP3628156A1 (en) 2018-09-28 2020-04-01 Basf Se Method for controlling pests of sugarcane, citrus, rapeseed, and potato plants
EP3628157A1 (en) 2018-09-28 2020-04-01 Basf Se Method of controlling insecticide resistant insects and virus transmission to plants
EP3628158A1 (en) 2018-09-28 2020-04-01 Basf Se Pesticidal mixture comprising a mesoionic compound and a biopesticide
BR112021004526A2 (en) 2018-09-28 2021-06-08 Basf Se use of compost, methods of plant protection, control or combating invertebrate pests, and seed and seed treatment
MX2021003430A (en) 2018-10-01 2021-06-15 Pi Industries Ltd Oxadiazoles as fungicides.
US20210392895A1 (en) 2018-10-01 2021-12-23 Pi Industries Limited Novel oxadiazoles
EP3643705A1 (en) 2018-10-24 2020-04-29 Basf Se Pesticidal compounds
WO2020095161A1 (en) 2018-11-05 2020-05-14 Pi Industries Ltd. Nitrone compounds and use thereof
EP3887357A1 (en) 2018-11-28 2021-10-06 Basf Se Pesticidal compounds
EP3670501A1 (en) 2018-12-17 2020-06-24 Basf Se Substituted [1,2,4]triazole compounds as fungicides
US20230031024A1 (en) 2018-12-18 2023-02-02 Basf Se Substituted pyrimidinium compounds for combating animal pests
EP3696177A1 (en) 2019-02-12 2020-08-19 Basf Se Heterocyclic compounds for the control of invertebrate pests
BR112021020232A2 (en) 2019-04-08 2021-12-07 Pi Industries Ltd Innovative Oxadiazole Compounds to Control or Prevent Phytopathogenic Fungi
KR20210150405A (en) 2019-04-08 2021-12-10 피아이 인더스트리스 엘티디. Novel oxadiazole compounds for controlling or preventing phytopathogenic fungi
MX2021012325A (en) 2019-04-08 2022-05-18 Pi Industries Ltd Novel oxadiazole compounds for controlling or preventing phytopathogenic fungi.
EP3730489A1 (en) 2019-04-25 2020-10-28 Basf Se Heteroaryl compounds as agrochemical fungicides
US20220202017A1 (en) 2019-05-29 2022-06-30 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2020244969A1 (en) 2019-06-06 2020-12-10 Basf Se Pyridine derivatives and their use as fungicides
WO2020244970A1 (en) 2019-06-06 2020-12-10 Basf Se New carbocyclic pyridine carboxamides
KR20220017940A (en) 2019-06-06 2022-02-14 바스프 에스이 fungicidal N-(pyrid-3-yl)carboxamide
EP3766879A1 (en) 2019-07-19 2021-01-20 Basf Se Pesticidal pyrazole derivatives
AR119774A1 (en) 2019-08-19 2022-01-12 Pi Industries Ltd OXADIAZOLE COMPOUNDS CONTAINING A 5-MEMBER HETEROAROMATIC RING TO CONTROL OR PREVENT PHYTOPATHOGENIC FUNGI
WO2021053136A1 (en) 2019-09-19 2021-03-25 Syngenta Crop Protection Ag Method for controlling fungus
WO2021063736A1 (en) 2019-10-02 2021-04-08 Basf Se Bicyclic pyridine derivatives
WO2021063735A1 (en) 2019-10-02 2021-04-08 Basf Se New bicyclic pyridine derivatives
AR120374A1 (en) 2019-11-08 2022-02-09 Pi Industries Ltd OXADIAZOLE COMPOUNDS CONTAINING FUSED HETEROCYCYL RINGS TO CONTROL OR PREVENT PHYTOPATHOGENIC FUNGI
JP2023507527A (en) 2019-12-23 2023-02-22 ビーエーエスエフ ソシエタス・ヨーロピア Enzyme-enhanced root uptake of pesticide compounds
GB202000994D0 (en) 2020-01-23 2020-03-11 Syngenta Crop Protection Ag Fungicidal compositions
EP4110057A1 (en) 2020-02-27 2023-01-04 Syngenta Crop Protection AG Fungicidal compositions
WO2021170463A1 (en) 2020-02-28 2021-09-02 BASF Agro B.V. Methods and uses of a mixture comprising alpha-cypermethrin and dinotefuran for controlling invertebrate pests in turf
BR112022017563A2 (en) 2020-03-04 2022-10-18 Basf Se USE OF COMPOUNDS, AGROCHEMICAL COMPOSITION AND METHOD TO FIGHT HARMFUL PHYTOPATOGENIC FUNGI
WO2021209360A1 (en) 2020-04-14 2021-10-21 Basf Se Fungicidal mixtures comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles
CN115460920A (en) 2020-04-28 2022-12-09 巴斯夫欧洲公司 Use of strobilurin-type compounds to control phytopathogenic fungi containing in the mitochondrial cytochrome b protein an amino acid substitution F129L conferring tolerance to Qo inhibitor II
EP3903582A1 (en) 2020-04-28 2021-11-03 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors ii
AU2021266044A1 (en) 2020-04-28 2022-11-24 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors IV
EP3903583A1 (en) 2020-04-28 2021-11-03 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors iii
EP3903581A1 (en) 2020-04-28 2021-11-03 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors i
EP4143167B1 (en) 2020-04-28 2024-05-15 Basf Se Pesticidal compounds
CA3170923A1 (en) 2020-04-28 2021-11-04 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors i
EP3903584A1 (en) 2020-04-28 2021-11-03 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors iv
CA3172204A1 (en) 2020-04-28 2021-11-04 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors ii
EP3909950A1 (en) 2020-05-13 2021-11-17 Basf Se Heterocyclic compounds for the control of invertebrate pests
EP4165017A1 (en) 2020-06-10 2023-04-19 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors v
EP3945089A1 (en) 2020-07-31 2022-02-02 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors v
WO2021249800A1 (en) 2020-06-10 2021-12-16 Basf Se Substituted [1,2,4]triazole compounds as fungicides
WO2022008303A1 (en) 2020-07-08 2022-01-13 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors vi
EP3939961A1 (en) 2020-07-16 2022-01-19 Basf Se Strobilurin type compounds and their use for combating phytopathogenic fungi
WO2022017836A1 (en) 2020-07-20 2022-01-27 BASF Agro B.V. Fungicidal compositions comprising (r)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1- (1,2,4-triazol-1-yl)propan-2-ol
EP3970494A1 (en) 2020-09-21 2022-03-23 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors viii
EP4195928A1 (en) 2020-08-11 2023-06-21 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors viii
AR123264A1 (en) 2020-08-18 2022-11-16 Pi Industries Ltd NEW HETEROCYCLIC COMPOUNDS TO COMBAT PHYTOPATHOGENIC FUNGI
UY39424A (en) 2020-09-15 2022-03-31 Pi Industries Ltd NEW PICOLINAMIDE COMPOUNDS TO COMBAT PHYTOPATHOGENIC FUNGI
AR123501A1 (en) 2020-09-15 2022-12-07 Pi Industries Ltd NEW PICOLINAMIDE COMPOUNDS TO COMBAT PHYTOPATHOGENIC FUNGI
AR123594A1 (en) 2020-09-26 2022-12-21 Pi Industries Ltd NEMATICIDAL COMPOUNDS AND THEIR USE
WO2022089969A1 (en) 2020-10-27 2022-05-05 BASF Agro B.V. Compositions comprising mefentrifluconazole
WO2022090071A1 (en) 2020-11-02 2022-05-05 Basf Se Use of mefenpyr-diethyl for controlling phytopathogenic fungi
WO2022090069A1 (en) 2020-11-02 2022-05-05 Basf Se Compositions comprising mefenpyr-diethyl
WO2022106304A1 (en) 2020-11-23 2022-05-27 BASF Agro B.V. Compositions comprising mefentrifluconazole
CN112812131B (en) * 2020-11-25 2022-06-21 广西民族师范学院 Preparation method and application of novel copper metal complex with two-dimensional structure
EP4018830A1 (en) 2020-12-23 2022-06-29 Basf Se Pesticidal mixtures
AR124796A1 (en) 2021-02-02 2023-05-03 Basf Se SYNERGIC ACTION OF DCD AND ALCOXYPYRAZOLES AS INHIBITORS OF NITRIFICATION
EP4043444A1 (en) 2021-02-11 2022-08-17 Basf Se Substituted isoxazoline derivatives
AR125764A1 (en) 2021-05-05 2023-08-09 Pi Industries Ltd NEW CONDENSED HETEROCYCLIC COMPOUNDS TO COMBAT PHYTOPATHOGENOUS FUNGI
EP4337012A1 (en) 2021-05-11 2024-03-20 Basf Se Fungicidal mixtures comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles
EP4088575A1 (en) 2021-05-14 2022-11-16 Hubert Sauter Method for the simultaneous optimization of ecology, economy and efficiency in the application of episystemic strobilurine fungicides
IL308534A (en) 2021-05-18 2024-01-01 Basf Se New substituted pyridines as fungicides
CA3219311A1 (en) 2021-05-18 2022-11-24 Basf Se New substituted quinolines as fungicides
CA3218900A1 (en) 2021-05-18 2022-11-24 Wassilios Grammenos New substituted pyridines as fungicides
CN117355504A (en) 2021-05-21 2024-01-05 巴斯夫欧洲公司 Use of ethynyl pyridine compounds as nitrification inhibitors
CN117440946A (en) 2021-05-21 2024-01-23 巴斯夫欧洲公司 Use of N-functionalized alkoxypyrazole compounds as nitrification inhibitors
AR125925A1 (en) 2021-05-26 2023-08-23 Pi Industries Ltd FUNGICIDAL COMPOSITION CONTAINING OXADIAZOLE COMPOUNDS
EP4094579A1 (en) 2021-05-28 2022-11-30 Basf Se Pesticidal mixtures comprising metyltetraprole
EP4358725A1 (en) 2021-06-21 2024-05-01 Basf Se Metal-organic frameworks with pyrazole-based building blocks
EP4119547A1 (en) 2021-07-12 2023-01-18 Basf Se Triazole compounds for the control of invertebrate pests
WO2023011958A1 (en) 2021-08-02 2023-02-09 Basf Se (3-pirydyl)-quinazoline
CN117794908A (en) 2021-08-02 2024-03-29 巴斯夫欧洲公司 (3-quinolinyl) -quinazolines
EP4140986A1 (en) 2021-08-23 2023-03-01 Basf Se Pyrazine compounds for the control of invertebrate pests
EP4140995A1 (en) 2021-08-27 2023-03-01 Basf Se Pyrazine compounds for the control of invertebrate pests
EP4151631A1 (en) 2021-09-20 2023-03-22 Basf Se Heterocyclic compounds for the control of invertebrate pests
WO2023072671A1 (en) 2021-10-28 2023-05-04 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors ix
WO2023072670A1 (en) 2021-10-28 2023-05-04 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors x
WO2023072672A1 (en) 2021-10-28 2023-05-04 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors xi
EP4194453A1 (en) 2021-12-08 2023-06-14 Basf Se Pyrazine compounds for the control of invertebrate pests
EP4198033A1 (en) 2021-12-14 2023-06-21 Basf Se Heterocyclic compounds for the control of invertebrate pests
EP4198023A1 (en) 2021-12-16 2023-06-21 Basf Se Pesticidally active thiosemicarbazone compounds
AR127972A1 (en) 2021-12-17 2024-03-13 Pi Industries Ltd NOVEL FUSED SUBSTITUTED BICYCLIC CARBOXAMIDE PYRIDINE COMPOUNDS TO COMBAT PHYTOPATHOGENIC FUNGI
EP4238971A1 (en) 2022-03-02 2023-09-06 Basf Se Substituted isoxazoline derivatives
EP4242199A1 (en) 2022-03-07 2023-09-13 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors xii
EP4242198A1 (en) 2022-03-07 2023-09-13 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors xiv
WO2023203066A1 (en) 2022-04-21 2023-10-26 Basf Se Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers
WO2023208447A1 (en) 2022-04-25 2023-11-02 Basf Se An emulsifiable concentrate having a (substituted) benzaldehyde-based solvent system
WO2024028243A1 (en) 2022-08-02 2024-02-08 Basf Se Pyrazolo pesticidal compounds
EP4342885A1 (en) 2022-09-20 2024-03-27 Basf Se N-(3-(aminomethyl)-phenyl)-5-(4-phenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-amine derivatives and similar compounds as pesticides
EP4361126A1 (en) 2022-10-24 2024-05-01 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors xv
WO2024104813A1 (en) 2022-11-14 2024-05-23 Basf Se Fungicidal mixture comprising substituted pyridines
WO2024104814A1 (en) 2022-11-16 2024-05-23 Basf Se Fungicidal mixture comprising substituted pyridines
WO2024104815A1 (en) 2022-11-16 2024-05-23 Basf Se Substituted benzodiazepines as fungicides
WO2024104818A1 (en) 2022-11-16 2024-05-23 Basf Se Substituted benzodiazepines as fungicides
WO2024104823A1 (en) 2022-11-16 2024-05-23 Basf Se New substituted tetrahydrobenzoxazepine
WO2024104822A1 (en) 2022-11-16 2024-05-23 Basf Se Substituted tetrahydrobenzodiazepine as fungicides
EP4389210A1 (en) 2022-12-21 2024-06-26 Basf Se Heteroaryl compounds for the control of invertebrate pests

Family Cites Families (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3325503A (en) 1965-02-18 1967-06-13 Diamond Alkali Co Polychloro derivatives of mono- and dicyano pyridines and a method for their preparation
US3296272A (en) 1965-04-01 1967-01-03 Dow Chemical Co Sulfinyl- and sulfonylpyridines
DE3338292A1 (en) 1983-10-21 1985-05-02 Basf Ag, 6700 Ludwigshafen 7-AMINO-AZOLO (1,5-A) -PYRIMIDINE AND FUNGICIDES CONTAINING THEM
CA1249832A (en) 1984-02-03 1989-02-07 Shionogi & Co., Ltd. Azolyl cycloalkanol derivatives and agricultural fungicides
DE3545319A1 (en) 1985-12-20 1987-06-25 Basf Ag ACRYLIC ACID ESTERS AND FUNGICIDES THAT CONTAIN THESE COMPOUNDS
MY100846A (en) 1986-05-02 1991-03-15 Stauffer Chemical Co Fungicidal pyridyl imidates
DE3782883T2 (en) 1986-08-12 1993-06-09 Mitsubishi Chem Ind PYRIDINE CARBOXAMIDE DERIVATIVES AND THEIR USE AS A FUNGICIDAL AGENT.
ES2097583T3 (en) * 1989-05-17 1997-04-01 Shionogi & Co PROCEDURE FOR THE PREPARATION OF ALCOXYIMINOACETAMIDE DERIVATIVES AND AN INTERMEDIARY OF THIS PROCEDURE.
AU628229B2 (en) 1989-11-10 1992-09-10 Agro-Kanesho Co. Ltd. Hexahydrotriazine compounds and insecticides
JP2828186B2 (en) 1991-09-13 1998-11-25 宇部興産株式会社 Acrylate-based compounds, their preparation and fungicides
WO1996036229A1 (en) * 1995-05-17 1996-11-21 E.I. Du Pont De Nemours And Company Fungicidal cyclic amides
IT1287161B1 (en) 1996-11-14 1998-08-04 Isagro Ricerca Srl ANALOGUE COMPOUNDS OF STROBYLURINS HAVING FUNGICIDE ACTIVITIES
DE19650197A1 (en) 1996-12-04 1998-06-10 Bayer Ag 3-thiocarbamoylpyrazole derivatives
TW460476B (en) 1997-04-14 2001-10-21 American Cyanamid Co Fungicidal trifluoromethylalkylamino-triazolopyrimidines
DE19731153A1 (en) 1997-07-21 1999-01-28 Basf Ag 2- (pyrazolyl- and triazolyl-3'-oxymethylene) -phenyl-isoxazolones and -triazolones, processes for their preparation and their use
CN1117074C (en) 1997-09-18 2003-08-06 巴斯福股份公司 Benzamidoxim derivatives, intermediate products and methods for preparing and using them as fungicides
DE19750012A1 (en) 1997-11-12 1999-05-20 Bayer Ag Isothiazole carboxamides
WO1999027783A1 (en) 1997-12-04 1999-06-10 Dow Agrosciences Llc Fungicidal compositions and methods, and compounds and methods for the preparation thereof
DE19900571A1 (en) 1998-01-24 1999-07-29 Basf Ag New oximino substituted phenyl tetrazolinone derivatives, having fungicidal, insecticidal, acaricidal and nematocidal activity
US6583090B1 (en) 1998-03-09 2003-06-24 Basf Aktiengesellschaft Hetaryl-substituted benzyl phenyl ethers, method for the production thereof, and their use for combating harmful fungi and animal pests
ATE305465T1 (en) 1998-11-17 2005-10-15 Kumiai Chemical Industry Co PYRIMIDINYLBENZIMIDAZOLE AND TRIAZINYLBENZIMIDAZOLE DERIVATIVES AND AGRICULT/HORTICULT FUNGICIDES
IT1303800B1 (en) 1998-11-30 2001-02-23 Isagro Ricerca Srl DIPEPTID COMPOUNDS HAVING HIGH FUNGICIDE AND AGRICULTURAL USE.
JP3417862B2 (en) 1999-02-02 2003-06-16 新東工業株式会社 Silica gel highly loaded with titanium oxide photocatalyst and method for producing the same
AU770077B2 (en) 1999-03-11 2004-02-12 Dow Agrosciences Llc Heterocyclic substituted isoxazolidines and their use as fungicides
US6586617B1 (en) 1999-04-28 2003-07-01 Sumitomo Chemical Takeda Agro Company, Limited Sulfonamide derivatives
UA73307C2 (en) 1999-08-05 2005-07-15 Куміаі Кемікал Індастрі Ко., Лтд. Carbamate derivative and fungicide of agricultural/horticultural destination
DE10021412A1 (en) 1999-12-13 2001-06-21 Bayer Ag Fungicidal active ingredient combinations
PL202070B1 (en) 2000-01-25 2009-05-29 Syngenta Participations Ag Herbicidal composition
US6376548B1 (en) 2000-01-28 2002-04-23 Rohm And Haas Company Enhanced propertied pesticides
IL167956A (en) 2000-02-04 2009-02-11 Sumitomo Chemical Co Isocyanate compound
BR0114122A (en) 2000-09-18 2003-07-01 Du Pont Compound, fungicidal compositions and method of controlling plant diseases caused by fungal plant pathogens
PT1341534E (en) 2000-11-17 2010-04-14 Dow Agrosciences Compounds having fungicidal activity and processes to make and use same
JP5034142B2 (en) 2001-04-20 2012-09-26 住友化学株式会社 Plant disease control composition
DE10136065A1 (en) 2001-07-25 2003-02-13 Bayer Cropscience Ag pyrazolylcarboxanilides
AR037228A1 (en) 2001-07-30 2004-11-03 Dow Agrosciences Llc ACID COMPOUNDS 6- (ARIL OR HETEROARIL) -4-AMYNOPYCOLINIC, HERBICIDE COMPOSITION THAT UNDERSTANDS AND METHOD TO CONTROL UNWANTED VEGETATION
FR2828196A1 (en) 2001-08-03 2003-02-07 Aventis Cropscience Sa New iodochromone derivatives, useful for the prevention or cure of plant fungal disorders, especially in cereals, vines, fruits, legumes or ornamental plants
AU2002327096B2 (en) 2001-08-17 2007-11-22 Sankyo Agro Company, Limited 3-phenoxy-4-pyridazinol derivative and herbicide composition containing the same
AU2002354251A1 (en) 2001-12-21 2003-07-09 Nissan Chemical Industries, Ltd. Bactericidal composition
TWI327462B (en) 2002-01-18 2010-07-21 Sumitomo Chemical Co Condensed heterocyclic sulfonyl urea compound, a herbicide containing the same, and a method for weed control using the same
DE10204390A1 (en) 2002-02-04 2003-08-14 Bayer Cropscience Ag Disubstituted thiazolylcarboxanilides
RU2323931C2 (en) 2002-03-05 2008-05-10 Синджента Партисипейшнс Аг O-cyclopropylcarboxanilides and application thereof as fungicides
GB0227966D0 (en) 2002-11-29 2003-01-08 Syngenta Participations Ag Organic Compounds
WO2004083193A1 (en) 2003-03-17 2004-09-30 Sumitomo Chemical Company, Limited Amide compound and bactericide composition containing the same
TWI355894B (en) 2003-12-19 2012-01-11 Du Pont Herbicidal pyrimidines
US9487519B2 (en) 2004-03-10 2016-11-08 Basf Se 5,6-Dialkyl-7-aminotriazolopyrimidines, their preparation and their use for controlling harmful fungi, and compositions comprising these compounds
AU2005221807A1 (en) 2004-03-10 2005-09-22 Basf Aktiengesellschaft 5,6-dialkyl-7-amino-triazolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said compounds
BRPI0510887A (en) 2004-06-03 2007-12-26 Du Pont fungicidal mixture, fungicidal composition and method for controlling plant diseases
JP2008502636A (en) 2004-06-18 2008-01-31 ビーエーエスエフ　アクチェンゲゼルシャフト N- (Ortho-phenyl) -1-methyl-3-difluoromethylpyrazole-4-carboxyanilide and their use as fungicides
DE502005009089D1 (en) 2004-06-18 2010-04-08 Basf Se 1-METHYL-3-TRIFLUOROMETHYL-PYRAZOLE-4-CARBOXYLIC ACID (ORTHO-PHENYL) -ANILIDES AND THEIR USE AS FUNGICIDES
GB0418048D0 (en) 2004-08-12 2004-09-15 Syngenta Participations Ag Method for protecting useful plants or plant propagation material
DE102005007160A1 (en) 2005-02-16 2006-08-24 Basf Ag Pyrazolecarboxylic acid anilides, process for their preparation and compositions containing them for controlling harmful fungi
ATE400576T1 (en) 2005-02-16 2008-07-15 Basf Se 5-ALKOXYALKYL-6-ALKYL-7-AMINO-AZOLOPYRIMIDINES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING HARMFUL FUNGALS AND AGENTS CONTAINING SAME
DE102005009458A1 (en) 2005-03-02 2006-09-07 Bayer Cropscience Ag pyrazolylcarboxanilides
AU2006307966B2 (en) * 2005-10-28 2012-03-22 Basf Se Method of inducing resistance to harmful fungi
CN102731381B (en) 2006-01-13 2016-08-17 美国陶氏益农公司 The polysubstituted aryl of 6-()-4-aminopyridine formic acid esters and the purposes as herbicide thereof
EP1983832A2 (en) 2006-02-09 2008-10-29 Syngeta Participations AG A method of protecting a plant propagation material, a plant, and/or plant organs
DE102007021853A1 (en) * 2007-05-10 2008-11-13 Norma Germany Gmbh Plug-in coupling and socket for a plug-in coupling
ES2552820T3 (en) * 2008-05-30 2015-12-02 Dow Agrosciences Llc Methods to combat QoI-resistant fungal pathogens
NZ598809A (en) 2009-09-01 2014-02-28 Dow Agrosciences Llc Synergistic fungicidal compositions containing a 5-fluoropyrimidine derivative for fungal control in cereals
PL3058824T3 (en) * 2010-08-05 2018-11-30 Bayer Cropscience Ag Active compound combinations comprising prothioconazole and fluxapyroxad for controlling corn diseases
US9271501B2 (en) 2011-12-21 2016-03-01 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi resistant to QO inhibitors

Also Published As

Publication number Publication date
AU2012358462A1 (en) 2014-07-10
IN2014CN04984A (en) 2015-09-18
IL232796A (en) 2016-03-31
EP2793579B1 (en) 2016-06-08
EP2793579A1 (en) 2014-10-29
CO7000781A2 (en) 2014-07-21
BR112014015535A8 (en) 2017-07-04
WO2013092224A1 (en) 2013-06-27
JP6189324B2 (en) 2017-08-30
JP2015509081A (en) 2015-03-26
KR20140107510A (en) 2014-09-04
CL2014001421A1 (en) 2014-09-12
CN104010502B (en) 2016-08-24
JP6430580B2 (en) 2018-11-28
US10080365B2 (en) 2018-09-25
ES2590466T7 (en) 2018-05-22
CR20140247A (en) 2014-07-23
DK2793579T3 (en) 2016-09-12
DK2793579T6 (en) 2018-05-28
HUE030004T2 (en) 2017-04-28
EA201400686A1 (en) 2014-12-30
KR102066829B1 (en) 2020-01-16
CA2856954C (en) 2020-09-22
JP2017197543A (en) 2017-11-02
ES2590466T3 (en) 2016-11-22
IL232796A0 (en) 2014-07-31
US9271501B2 (en) 2016-03-01
MX2014006517A (en) 2015-02-17
PT2793579T (en) 2016-07-18
PL2793579T3 (en) 2016-12-30
PL2793579T6 (en) 2018-08-31
US20160249615A1 (en) 2016-09-01
CA2856954A1 (en) 2013-06-27
CN104010502A (en) 2014-08-27
US20140323305A1 (en) 2014-10-30
BR112014015535A2 (en) 2017-06-13
EA024331B1 (en) 2016-09-30
PE20141431A1 (en) 2014-10-29
EP2793579B3 (en) 2018-02-14
ZA201404495B (en) 2015-12-23

Similar Documents

Publication Publication Date Title
US10080365B2 (en) Use of strobilurin type compounds for combating phytopathogenic fungi resistant to Qo inhibitors
US10442777B2 (en) Use of substituted oxadiazoles for combating phytopathogenic fungi
US10492494B2 (en) Substituted oxadiazoles for combating phytopathogenic fungi
US10555526B2 (en) Substituted oxadiazoles for combating phytopathogenic fungi
US10687532B2 (en) Substituted oxadiazoles for combating phytopathogenic fungi
US9173402B2 (en) Fungicidal alkyl-substituted 2[2-chloro-4-(4-chioro-phenoxy)-phenyl]-1[1,2,4]triazol-1-yl-ethanol compounds
US20180317489A1 (en) Substituted Oxadiazoles for Combating Phytopathogenic Fungi
US20180317488A1 (en) Use of Substituted Oxadiazoles for Combating Phytopathogenic Fungi
US20140141974A1 (en) Fungicidal phenylalkyl-substituted 2-[2-chloro-4-(4-chloro-phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
AU2012296887A1 (en) Fungicidal substituted 1-{2-[2-halo-4-(4-halogen-phenoxy)-phenyl]-2-alkoxy-3-methyl-butyl}-1H-[1,2,4]triazole compounds
US20140155262A1 (en) Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
US10071971B2 (en) Substituted [1,2,4]triazole compounds and their use as fungicides
US9137997B2 (en) Use of substituted dithiine-dicarboximides for combating phytopathogenic fungi
AU2012358462B2 (en) Use of strobilurin type compounds for combating phytopathogenic fungi resistant to Qo inhibitors
US20110039693A1 (en) Pyrimidylmethyl Sulfonamide Compounds
EP2815648A1 (en) Novel strobilurin-type compounds for combating phytopathogenic fungi

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: ADVISORY ACTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION