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WO2025211272A1 - Pesticidal mixtures comprising an ethylsulfone compound - Google Patents

Pesticidal mixtures comprising an ethylsulfone compound

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Publication number
WO2025211272A1
WO2025211272A1 PCT/JP2025/012748 JP2025012748W WO2025211272A1 WO 2025211272 A1 WO2025211272 A1 WO 2025211272A1 JP 2025012748 W JP2025012748 W JP 2025012748W WO 2025211272 A1 WO2025211272 A1 WO 2025211272A1
Authority
WO
WIPO (PCT)
Prior art keywords
spp
mixture
compound
mixtures
component
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.)
Pending
Application number
PCT/JP2025/012748
Other languages
French (fr)
Inventor
Daniel A. Whalen
Anna CHAPMAN
Hiroshi Inui
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.)
Nihon Nohyaku Co Ltd
Original Assignee
Nihon Nohyaku Co Ltd
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Filing date
Publication date
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Publication of WO2025211272A1 publication Critical patent/WO2025211272A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • A01N43/72—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
    • 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
    • A01N37/46—N-acyl derivatives
    • 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
    • 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
    • A01N47/02—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 no bond to a nitrogen 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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • In.20 Thiodicarb and In.39:Abamectin are insecticides, but belong at the same time to group N (nematicides).
  • F.10 Fluopyram and F.19: Cyclobutrifluram are fungicides, but belong at the same time to group N (nematicides).
  • the mixtures according to the invention may be a physical mixture of the compound I and the at least one compound II. Accordingly, the invention also provides a mixture comprising compound I and at least one compound II. However, the composition may also be any combination of compound I with at least one compound II, it not being required for compounds A and B to be present together in the same formulation.
  • An example of a composition according to the invention or to be used according to the invention in which the compound I and the at least one compound II are not present together in the same formulation is a combipack. In a combipack, two or more components of a combipack are packaged separately, i.e., not jointly pre-formulated.
  • invertebrate pest also referred to as animal pests
  • animal pests encompasses animal populations, such as insects, arachnids and nematodes, which may attack plants, thereby causing substantial damage to the plants attacked, as well as ectoparasites which may infest animals, in particular warm-blooded animals such as e.g. mammals or birds, or other higher animals such as reptiles, amphibians or fish, thereby causing substantial damage to the animals infested.
  • compound according to the invention or “compound of formula I” or “compound I” comprises the compound as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof.
  • stereoisomers encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
  • the compound of formula I-1 has a stereocenter and thus exists in enantiomers (stereoisomers).
  • the compound of formula I-1 is used either as a mixture of the two enantiomers, as a racemate (1:1 mixture of the two enantiomers) or as a pure enantiomer (R- or S-enantiomer).
  • the compounds of the invention may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities.
  • the invention includes both amorphous and crystalline compounds of the formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula I are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound I has a basic functionality or by reacting an acidic compound I with a suitable base.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C 1 -C 4 -alkyl)sulfonium, and sulfoxonium ions, preferably tri(C 1 -C 4 -alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, 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 formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
  • Clariva (trademark) PN from Syngenta Crop Protection, LLC, USA).
  • N.7 Burkholderia rinojensis A 396: Burkholderia sp. A396 isolated from soil in Nikko, Japan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc., USA).
  • N.8 Bacillus firmus I1582 (VOTIVO): B. firmus CNCM I-1582, a variant of parental strain EIP-N1 (CNCM I-1556) isolated from soil of central plain area of Israel (WO 2009/126473, US6,406,690; e.g. Votivo (trademark registered) from Bayer CropScience LP, USA).
  • N.16 Bacillus amyloliquefaciens velezensis MBI600: B. a. ssp. plantarum or B. vele-zensis MBI600 isolated from faba bean in Sutton Bonington, Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRL B 50595; US 2012/0149571 A1; e.g. Integral (trademark registered)from BASF Corp., USA).
  • the solid material (dry matter) of the biopesticides (with the ex-ception of oils e.g. Neem oil) are considered as active components (e.g. to be obtained after drying or evaporation of the extraction or suspension medium in case of liquid formulations of the microbial pesticides).
  • the weight ratios and percentages used herein for a biological extract e.g. Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).
  • the total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including dormant forms can be determined using the amount of CFU of the respective microorganism to calculate the total weight of the respective active component with the following equation that 1x10 10 CFU equals one gram of total weight of the respective active component.
  • Colony forming unit is measure of viable microbial cells, in particular fungal and bacterial cells.
  • CFU may also be understood as the number of (juvenile) individual nematodes in case of (entomo-pathogenic) nematode biopesticides, e.g. Steinernema feltiae.
  • the application rates range from 1x10 6 to 5x10 16 (or more) CFU/ha, preferably from 1x10 8 to 1x10 13 CFU/ha, and even more preferably from 1x10 9 to 5x10 15 CFU/ha and in particular from 1x10 12 to 5x10 14 CFU/ha.
  • the application rates regularly range from 1x10 5 to 1x10 12 (or more), preferably from 1x10 8 to 1x10 11 , more preferably from 5x10 8 to 1x10 10 individuals (e.g.
  • the compound I can be used as synergists for certain insecticidal and fungicidal active compounds. By simultaneous, that is joint or separate, application of the compound I with at least one active compound II, the insecticidal or fungicidal activity is increased in a superadditive manner.
  • the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from F.1:-Azoxystrobin, F.2:-Trifloxystrobin, F.3:-Picoxystrobin, F.4:-Pyraclostrobin, F.5:-Mandestrobin, F.66: fluoxastrobin, F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-Isoflucypram, F.19:-Cyclobutrifluram, F.20:-Ox
  • N.10 Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo)
  • N.11 Bacillus licheniformis FMCH001
  • N.12 Bacillus subtilis FMCH002
  • N.11 + N.12 (Presence/Avodigen)
  • N.13 Chromobacterium subtsugae PRAA4-T1, N.14: B.
  • the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from F.4:-Pyraclostrobin, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.22:-Metalaxyl, F.31:-Flutriafol, F.35:-Mefentrifluconazole, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.42:-Fludioxinil, F.43:-Thiabendazole, F.45:-Fluazinam, F.49:-Thiophanate-methyl, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil; In.1: Clothianidin
  • the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from F.1:-Azoxystrobin, F.2:-Trifloxystrobin, F.3:-Picoxystrobin, F.4:-Pyraclostrobin, F.5:-Mandestrobin, F.66: fluoxastrobin, F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.9:-Bixafen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.15:-Fluindapyr, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-
  • a component B) selected from F.1
  • the invention relates to mixtures of compound formula I-1 with a component B selected from fungicides F.1:-Azoxystrobin, F.2:-Trifloxystrobin, F.3:-Picoxystrobin, F.4:-Pyraclostrobin, F.5:-Mandestrobin, F.66: fluoxastrobin, F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-Isoflucypram, F.19:-Cyclobutrifluram, F.20:-Oxathiapiprol, F
  • the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from F.4:-Pyraclostrobin, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.22:-Metalaxyl, F.31:-Flutriafol, F.35:-Mefentrifluconazole, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.42:-Fludioxinil, F.43:-Thiabendazole, F.45:-Fluazinam, F.49:-Thiophanate-methyl, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil.
  • a component B) selected from F.4:-
  • the invention relates to mixtures of compound formula I-1 with a component B selected from the SDHI inhibitors F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-Isoflucypram, F.19:-Cyclobutrifluram.
  • a component B selected from the SDHI inhibitors F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-
  • the invention relates to mixtures of compound formula I-1 with a component B selected from the DMI fungicides (azoles) F.29:-Difenoconazole, F.30:-Prothioconazole, F.31:-Flutriafol, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.41:-Fluoxytioconazole.
  • a component B selected from the DMI fungicides (azoles) F.29:-Difenoconazole, F.30:-Prothioconazole, F.31:-Flutriafol, F.32:
  • the invention relates to mixtures of of compound formula I-1 with a component B selected from the DMI fungicides (azoles) F.29:-Difenoconazole, F.30:-Prothioconazole, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.39:-Triticonazole, F.41:-Fluoxytioconazole.
  • a component B selected from the DMI fungicides (azoles) F.29:-Difenoconazole, F.30:-Prothioconazole, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.39:-
  • the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from insecticides In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.4: Dinotefuran, In.5: Thiacloprid, In.6: Acetamiprid, In.7: Sulfoxaflor, In.8: Flupyradifurone, In.9: Triflumezopyrim, In.10: Dicloromezotiaz , In.11: Fenmezoditiaz, In.12: Flupyrimin, In.13: Tefluthrin, In.14: Bifenthrin, In.15: Cypermethrin, In.16: alpha-Cypermethrin, In.17: zeta-Cypermethrin, In.18: lambda-Cyhalothrin, In.1: Clothianidin, In.2:
  • the invention relates to mixtures of compound formula I-1 with a component B selected from insecticides In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.4: Dinotefuran, In.6: Acetamiprid, In.8: Flupyradifurone, In.12: Flupyrimin, In.13: Tefluthrin, In.14: Bifenthrin, In.19: beta-Cyfluthrin, In.20: Thiodicarb, In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.25: Tetraniliprole, In.26: Cyclaniliprole, In.27: Fipronil, In.28: Isocycloseram, In.30: Broflanilide, In.31: Nicofluprole, In.32: Tigolaner, In.33: Dimpropyridaz, In.39: Abamam
  • the invention relates to mixtures of compound formula I-1 with a component B selected from the pyrethroids In.13: Tefluthrin, In.14: Bifenthrin, In.19: beta-Cyfluthrin.
  • the invention relates to mixtures of compound formula I-1 with a component B selected from the diamides In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.25: Tetraniliprole, In.26: Cyclaniliprole.
  • the invention relates to mixtures of compound formula I-1 with a component B which is In.27: Fipronil.
  • the invention relates to mixtures of compound formula I-1 with a component B selected from the insecticides In.28: Isocycloseram and In.30: Broflanilide.
  • the invention relates to mixtures of compound formula I-1 with a component B selected from the insecticides In.20: Thiodicarb, In.31: Nicofluprole, In.32: Tigolaner, In.33: Dimpropyridaz, In.39: Abamectin, In.49: Oxazosulfyl.
  • the invention relates to mixtures of compound formula I-1 with a component B selected from the insecticides clothianidin, broflanilide, chlorantraniliprole, fipronil; preferably clothianidin.
  • EX297512 N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.16: Bacillus amyloliquefaciens velezensis MBI600.
  • the invention relates to mixtures of compound formula I-1 with a component B selected from nematicides In.20: Thiodicarb, In.39: Abamectin, F.10: Fluopyram, F.19: Cyclobutrifluram, N.1: Tioxazafen, N.5: Sulfiflumin, N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), N.9: B.
  • a component B selected from nematicides In.20: Thiodicarb, In.39: Abamectin, F.10: Fluopyram, F.19: Cyclobutrifluram, N.1: Tioxazafen, N.5: Sulfiflumin, N.6: Pasteuria nishizawae (Clariva), N.7: Bur
  • EX297512 N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.16: Bacillus amyloliquefaciens velezensis MBI600.
  • the invention relates to mixtures of compound formula I-1 with a component B selected from nematicides, N.1: Tioxazafen, N.2: Fluazaindolizine, N.3: Flufensulfone, N.4: Flupentiofenox, N.5: Sulfiflumin, N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), F.10 Fluopyram + N.8, N.9: B.
  • a component B selected from nematicides, N.1: Tioxazafen, N.2: Fluazaindolizine, N.3: Flufensulfone, N.4: Flupentiofenox, N.5: Sulfiflumin, N.6: Pasteuria nishizawae (Clariva), N.
  • N.10 Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo)
  • N.11 Bacillus licheniformis FMCH001
  • N.12 Bacillus subtilis FMCH002
  • N.11 + N.12 (Presence/Avodigen)
  • N.13 Chromobacterium subtsugae PRAA4-T1, N.14: B.
  • amyloliquefaciens F727, N.15 Rootella (trademark) mycorrhizae, N.13 + N.7 + N.14 + N.15 (BSST), N.16: Bacillus amyloliquefaciens velezensis MBI600, N.16 + cis-jasmone.
  • the invention relates to mixtures of compound formula I-1 with a component B selected from nematicides N.1: Tioxazafen, N.2: Fluazaindolizine, N.3: Flufensulfone, N.4: Flupentiofenox, N.5: Sulfiflumin.
  • the invention relates to mixtures of compound formula I-1 with a component B selected from nematicides N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), N.9: B. thuringiensis EX297512, N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B.
  • a component B selected from nematicides
  • N.6 Pasteuria nishizawae (Clariva)
  • N.7 Burkholderia rinojensis A 396
  • N.8 Bacillus firmus
  • amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.16: Bacillus amyloliquefaciens velezensis MBI600.
  • the invention relates to mixtures of compound formula I-1 with a component B selected from biopesticides N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), F.10 Fluopyram + N.8, N.9: B.
  • the mixture of the invention is one of the mixtures selected from mixtures M-1 to M-135:
  • the invention relates to a mixture of compound I-1 with F.1 (mixture M-1).
  • the invention relates to a mixture of compound I-1 with F.2 (mixture M-2).
  • the invention relates to a mixture of compound I-1 with F.3 (mixture M-3).
  • the invention relates to a mixture of compound I-1 with F.4 (mixture M-4).
  • the invention relates to a mixture of compound I-1 with F.5 (mixture M-5).
  • the invention relates to a mixture of compound I-1 with F.6 (mixture M-6).
  • the invention relates to a mixture of compound I-1 with F.14 (mixture M-14). In one aspect, the invention relates to a mixture of compound I-1 with F.15 (mixture M-15). In one aspect, the invention relates to a mixture of compound I-1 with F.16 (mixture M-16). In one aspect, the invention relates to a mixture of compound I-1 with F.17 (mixture M-17). In one aspect, the invention relates to a mixture of compound I-1 with F.18 (mixture M-18). In one aspect, the invention relates to a mixture of compound I-1 with F.19 (mixture M-19). In one aspect, the invention relates to a mixture of compound I-1 with F.20 (mixture M-20).
  • the invention relates to a mixture of compound I-1 with F.21 (mixture M-21). In one aspect, the invention relates to a mixture of compound I-1 with F.22 (mixture M-22). In one aspect, the invention relates to a mixture of compound I-1 with F.23 (mixture M-23). In one aspect, the invention relates to a mixture of compound I-1 with F.24 (mixture M-24). In one aspect, the invention relates to a mixture of compound I-1 with F.25 (mixture M-25). In one aspect, the invention relates to a mixture of compound I-1 with F.26 (mixture M-26). In one aspect, the invention relates to a mixture of compound I-1 with F.27 (mixture M-27).
  • the invention relates to a mixture of compound I-1 with F.28 (mixture M-28). In one aspect, the invention relates to a mixture of compound I-1 with F.29 (mixture M-29). In one aspect, the invention relates to a mixture of compound I-1 with F.30 (mixture M-30). In one aspect, the invention relates to a mixture of compound I-1 with F.31 (mixture M-31). In one aspect, the invention relates to a mixture of compound I-1 with F.32 (mixture M-32). In one aspect, the invention relates to a mixture of compound I-1 with F.33 (mixture M-33). In one aspect, the invention relates to a mixture of compound I-1 with F.34 (mixture M-34).
  • the invention relates to a mixture of compound I-1 with F.35 (mixture M-35). In one aspect, the invention relates to a mixture of compound I-1 with F.36 (mixture M-36). In one aspect, the invention relates to a mixture of compound I-1 with F.37 (mixture M-37). In one aspect, the invention relates to a mixture of compound I-1 with F.38 (mixture M-38). In one aspect, the invention relates to a mixture of compound I-1 with F.39 (mixture M-39). In one aspect, the invention relates to a mixture of compound I-1 with F.40 (mixture M-40). In one aspect, the invention relates to a mixture of compound I-1 with F.41 (mixture M-41).
  • the invention relates to a mixture of compound I-1 with F.42 (mixture M-42). In one aspect, the invention relates to a mixture of compound I-1 with F.43 (mixture M-43). In one aspect, the invention relates to a mixture of compound I-1 with F.44 (mixture M-44). In one aspect, the invention relates to a mixture of compound I-1 with F.45 (mixture M-45). In one aspect, the invention relates to a mixture of compound I-1 with F.46 (mixture M-46). In one aspect, the invention relates to a mixture of compound I-1 with F.47 (mixture M-47). In one aspect, the invention relates to a mixture of compound I-1 with F.48 (mixture M-48).
  • the invention relates to a mixture of compound I-1 with F.49 (mixture M-49). In one aspect, the invention relates to a mixture of compound I-1 with F.50 (mixture M-50). In one aspect, the invention relates to a mixture of compound I-1 with F.51 (mixture M-51). In one aspect, the invention relates to a mixture of compound I-1 with F.52 (mixture M-52). In one aspect, the invention relates to a mixture of compound I-1 with F.53 (mixture M-53). In one aspect, the invention relates to a mixture of compound I-1 with F.54 (mixture M-54). In one aspect, the invention relates to a mixture of compound I-1 with F.55 (mixture M-55).
  • the invention relates to a mixture of compound I-1 with F.56 (mixture M-56). In one aspect, the invention relates to a mixture of compound I-1 with F.57 (mixture M-57). In one aspect, the invention relates to a mixture of compound I-1 with F.58 (mixture M-58). In one aspect, the invention relates to a mixture of compound I-1 with F.59 (mixture M-59). In one aspect, the invention relates to a mixture of compound I-1 with F.60 (mixture M-60). In one aspect, the invention relates to a mixture of compound I-1 with F.61 (mixture M-61). In one aspect, the invention relates to a mixture of compound I-1 with F.62 (mixture M-62).
  • the invention relates to a mixture of compound I-1 with F.63 (mixture M-63). In one aspect, the invention relates to a mixture of compound I-1 with F.64 (mixture M-64). In one aspect, the invention relates to a mixture of compound I-1 with F.65 (mixture M-65). In one aspect, the invention relates to a mixture of compound I-1 with In.1 (mixture M-66). In one aspect, the invention relates to a mixture of compound I-1 with In.2 (mixture M-67). In one aspect, the invention relates to a mixture of compound I-1 with In.3 (mixture M-68). In one aspect, the invention relates to a mixture of compound I-1 with In.4 (mixture M-69).
  • the invention relates to a mixture of compound I-1 with In.5 (mixture M-70). In one aspect, the invention relates to a mixture of compound I-1 with In.6 (mixture M-71). In one aspect, the invention relates to a mixture of compound I-1 with In.7 (mixture M-72). In one aspect, the invention relates to a mixture of compound I-1 with In.8 (mixture M-73). In one aspect, the invention relates to a mixture of compound I-1 with In.9 (mixture M-74). In one aspect, the invention relates to a mixture of compound I-1 with In.10 (mixture M-75). In one aspect, the invention relates to a mixture of compound I-1 with In.11 (mixture M-76).
  • the invention relates to a mixture of compound I-1 with In.19 (mixture M-84). In one aspect, the invention relates to a mixture of compound I-1 with In.20 (mixture M-85). In one aspect, the invention relates to a mixture of compound I-1 with In.21 (mixture M-86). In one aspect, the invention relates to a mixture of compound I-1 with In.22 (mixture M-87). In one aspect, the invention relates to a mixture of compound I-1 with In.23 (mixture M-88). In one aspect, the invention relates to a mixture of compound I-1 with In.24 (mixture M-89). In one aspect, the invention relates to a mixture of compound I-1 with In.25 (mixture M-90).
  • the invention relates to a mixture of compound I-1 with In.26 (mixture M-91). In one aspect, the invention relates to a mixture of compound I-1 with In.27 (mixture M-92). In one aspect, the invention relates to a mixture of compound I-1 with In.28 (mixture M-93). In one aspect, the invention relates to a mixture of compound I-1 with In.29 (mixture M-94). In one aspect, the invention relates to a mixture of compound I-1 with In.30 (mixture M-95). In one aspect, the invention relates to a mixture of compound I-1 with In.31 (mixture M-96). In one aspect, the invention relates to a mixture of compound I-1 with In.32 (mixture M-97).
  • the invention relates to a mixture of compound I-1 with In.33 (mixture M-98). In one aspect, the invention relates to a mixture of compound I-1 with In.34 (mixture M-99). In one aspect, the invention relates to a mixture of compound I-1 with In.35 (mixture M-100). In one aspect, the invention relates to a mixture of compound I-1 with In.36 (mixture M-101). In one aspect, the invention relates to a mixture of compound I-1 with In.37 (mixture M-102). In one aspect, the invention relates to a mixture of compound I-1 with In.38 (mixture M-103). In one aspect, the invention relates to a mixture of compound I-1 with In.39 (mixture M-104).
  • the invention relates to a mixture of compound I-1 with In.47 (mixture M-112). In one aspect, the invention relates to a mixture of compound I-1 with In.48 (mixture M-113). In one aspect, the invention relates to a mixture of compound I-1 with In.49 (mixture M-114). In one aspect, the invention relates to a mixture of compound I-1 with N.1 (mixture M-115). In one aspect, the invention relates to a mixture of compound I-1 with N.2 (mixture M-116). In one aspect, the invention relates to a mixture of compound I-1 with N.3 (mixture M-117). In one aspect, the invention relates to a mixture of compound I-1 with N.4 (mixture M-118).
  • the invention relates to a mixture of compound I-1 with N.5 (mixture M-119). In one aspect, the invention relates to a mixture of compound I-1 with N.6 (mixture M-120). In one aspect, the invention relates to a mixture of compound I-1 with N.7 (mixture M-121). In one aspect, the invention relates to a mixture of compound I-1 with N.8 (mixture M-122). In one aspect, the invention relates to a mixture of compound I-1 with F.10. + N.8 (mixture M-123). In one aspect, the invention relates to a mixture of compound I-1 with N.9 (mixture M-124).
  • the invention relates to a mixture of compound I-1 with N.8: + N.9 (mixture M-125). In one aspect, the invention relates to a mixture of compound I-1 with N.10 (mixture M-126). In one aspect, the invention relates to a mixture of compound I-1 with N.11 (mixture M-127). In one aspect, the invention relates to a mixture of compound I-1 with N.12 (mixture M-128). In one aspect, the invention relates to a mixture of compound I-1 with N.11: + N.12 (mixture M-129). In one aspect, the invention relates to a mixture of compound I-1 with N.13 (mixture M-130).
  • the mixtures of the invention are binary mixtures of the compound I and a compound II.
  • the mixtures of the invention are mixtures comprising at least one further pesticide, i.e. higher mixtures.
  • the further pesticides are selected from the group as given for component B herein, with the proviso that no two of of the pesticides are identical. If there are more than two pesticides present in a mixture according to the invention, the weight ratio of each of the components to the other components is in the ratio ranges as given for the ratios of two pesticides, i.e.
  • the mixtures of the invention are mixtures of I-1 (component A) and a compound II (component B) and a further compound II (component C), wherein the component C is selected from the same group of compounds as component B, with the proviso that component B and C are not identical.
  • These mixtures comprise at least three active compounds.
  • the mixtures of the invention consist of three active compounds (A, B, C), i.e. three-way mixtures.
  • the mixtures of the invention may comprise further active compounds beyond these three components.
  • the pesticides B and C, with which compound I-1 are mixed may be two fungicides, or an insecticide and a fungicide, or an insecticide and a nematicide.
  • Table T the following mixtures of Table T are part of the invention:
  • the mixtures of the invention are mixtures of I-1 and a further compound, comprising two further pesticides, i.e. four-way mixtures.
  • the mixtures of the invention are mixtures of I-1 with a compound II (component B), which comprise two further compounds II (component C and D), wherein the the components C and D are selected from the same group of compounds as component B, with the proviso that none of components B, C and D are identical.
  • the mixtures of the invention are mixtures of each three-way mixture of Table T above, which further comprise one of the pesticides as given for component B.
  • the mixtures of the invention are mixtures comprising three further pesticides, i.e. five-way mixtures.
  • the mixtures of the invention are mixtures of each three-way mixture of Table T above, which further comprise two of the pesticides as given in the list for component B.
  • the invention also relates to agrochemical compositions comprising an auxiliary and a mixture of the invention.
  • An agrochemical composition comprises a pesticidally effective amount of a mixture of the invention.
  • the compound I and its mixtures can be converted into customary types of agro-chemical 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.
  • 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, e.g.
  • 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.
  • Suitable solid carriers or fillers are mineral earths.
  • Suitable surfactants are surface-active compounds, e.g. anionic, cationic, nonionic, and amphoteric surfactants, block polymers, polyelectrolytes. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants.
  • Suitable cationic surfactants are qua-ternary surfactants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably 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%.
  • the mixtures of the invention are suitable for use in protecting crops, plants, plant propagation materials, e.g. seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, e.g. seeds, or soil or water, in which the plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of a mixture of the invention.
  • the mixtures of the invention are also suitable for use in combating or controlling animal pests.
  • the invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, e.g. seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a mixture of the invention.
  • the mixtures of the invention are effective through both contact and ingestion to any and all developmental stages, such as egg, larva, pupa, and adult.
  • the mixtures of the invention can be applied as such or in form of compositions comprising them. The application can be carried out both before and after the infestation of the crops, plants, plant propagation materials by the pests.
  • the term "contacting" includes both direct contact (applying the compounds/compositions directly on the animal pest or plant) and indirect contact (applying the compounds/compositions to the locus).
  • animal pest includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects.
  • plant includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g. sugar beet, or fodder beet; fruits, e.g.
  • Herbicide tolerance has been created by using mutagenesis as well as using genetic engineering. Plants which have been rendered tolerant to ALS inhibitor herbicides by conventional methods of mutagenesis and breeding comprise plant varieties commercially available under the name Clearfield (trademark registered) . Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides and HPPD inhibitors, like isoxaflutole and mesotrione.
  • Transgenic canola events comprising herbicide tolerance genes are e.g., but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.
  • Insect resistance has mainly been created by transferring bacterial genes for insecticidal pro-teins to plants.
  • Transgenes which have most frequently been used are toxin genes of Bacillus spec.
  • genes of plant origin have been transferred to other plants.
  • genes coding for protease inhibitors like CpTI and pinII.
  • a further approach uses transgenes in order to produce double stranded RNA in plants to target and downregulate in-sect genes.
  • An example for such a transgene is dvsnf7.
  • Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA are e.g., but not excluding others, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098.
  • Transgenic soybean events comprising genes for insecticidal proteins are e.g., but not excluding others, MON87701, MON87751 and DAS-81419.
  • Transgenic cotton events comprising genes for insecticidal proteins are e.g., but not excluding others, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.
  • Increased yield has been created by increasing ear biomass using the transgene athb17, be-ing present in corn event MON87403, or by enhancing photosynthesis using the transgene bbx32, being present in the soybean event MON87712.
  • Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.
  • Tolerance to abiotic conditions, in particular to tolerance to drought, has been created by using the transgene cspB, comprised by the corn event MON87460 and by using the transgene Hahb-4, comprised by soybean event IND-00410-5. Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process.
  • Preferred combination of traits are herbicide tolerance to different groups of herbicides, insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, herbicide tolerance with one or several types of insect resistance, herbicide tolerance with increased yield as well as a combination of herbicide tolerance and tolerance to abiotic conditions.
  • Plants comprising singular or stacked traits as well as the genes and events providing these traits are known (http://www.isaaa.org/gmapprovaldatabase) and (http://cera-gmc.org/GMCropDatabase).
  • compositions according to the invention on cultivated plants may result in effects which are specific to a cultivated plant comprising a certain gene or event. These effects may comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigor, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content. It has been found that the pesticidal activity of the mixtures of the invention may be enhanced by the insecticidal trait of a modified plant.
  • the mixtures of the invention are suitable for preventing insects to become resistant to the insecticidal trait or for combating pests, which already have become resistant to the insecticidal trait of a modified plant. Moreover, the mixtures of the invention are suitable for combating pests, against which the insecticidal trait is not effective, so that a complementary insecticidal activity can advantageously be used.
  • plant propagation material refers to all the generative parts of the plant e.g. seeds and vegetative plant material e.g. 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.
  • Attagenus spp. Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. e.g. B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Callopistria floridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp. e.g. C. assimilis, C.
  • insects from the order of Diptera e.g. Aedes spp. e.g. A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. e.g. A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A.
  • Heliothrips spp. Hercinothrips femoralis, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. e.g. S. citri, S. dorsalis, S. perseae; Stenchaetothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp. e.g. T. imagines, T. hawaiiensis, T.
  • insects from the order of Hemiptera e.g., Acizzia jamatonica, Acrosternum spp., e.g. A. hilare; Acyrthosipon spp., e.g. A. onobrychis, A. pisum; Adelges laricis, Adelges tsugae, Adelphocoris spp., e.g. A. rapidus, A.
  • D. citri Diaspis spp. e.g. D. bromeliae; Dichelops furcatus, Diconocoris hewetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. e.g. D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. e.g. D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empoasca spp.
  • P. comstocki Psylla spp. e.g. P. mali; Pteromalus spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., e.g. Q. perniciosus; Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. e.g. R. pseudobrassicas, R. insertum, R. maidis, R.
  • Acanthomyops interjectus Athalia rosae, Atta spp. e.g. A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A. sexdens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp. e.g. C. floridanus, C. pennsylvanicus, C.
  • Gryllotalpa spp. e.g. G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. e.g. L. migratoria, L. pardalina; Melanoplus spp. e.g. M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M.
  • Boophilus spp. e.g. B. annulatus, B. decoloratus, B. microplus, Dermacentor spp. e.g. D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. e.g. H. truncatum, Ixodes spp. e.g. I. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp. e.g. O. moubata, O. hermsi, O.
  • Aculus spp. e.g. A. Anatoma spp.
  • Colomerus vitis Epitrimerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp. e.g. Eriophyes sheldoni
  • Family Tarsonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Stenotarsonemus spp. Steneotarsonemus spinki
  • Family Tenuipalpidae including Brevipalpus spp. e.g. B.
  • Tetranychidae including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp. e.g. T. cinnabarinus, T. evansi, T. kanzawai, T, pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praetiosa; Panonychus spp. e.g. P. ulmi, P. citri; Metatetranychus spp. and Oligonychus spp. e.g. O. pratensis, O.
  • root-knot nematodes Meloidogyne spp. e.g. M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. e.g. G. rostochiensis; Heterodera spp. e.g. H. avenae, H. glycines, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelenchoides spp. e.g. A. besseyi; Sting nematodes, Belonolaimus spp.
  • Awl nematodes Dolichodorus spp.
  • Spiral nematodes Heliocotylenchus multicinctus
  • Sheath and sheathoid nematodes Hemicycliophora spp. and Hemicriconemoides spp.
  • Hirshmanniella spp. Lance nematodes, Hoploaimus spp.
  • False rootknot nematodes Nacobbus spp.
  • Needle nematodes Longidorus spp. e.g. L. elongatus
  • Lesion nematodes Pratylenchus spp. e.g. P.
  • Stunt nematodes Tylenchorhynchus spp. e.g. T. claytoni, T. dubius
  • Citrus nematodes Tylenchulus spp. e.g. T. semipenetrans
  • Dagger nematodes Xiphinema spp.
  • other plant parasitic nematode species Insects from the order Blattodea e.g. Macrotermes spp. e.g. M. natalensis
  • Cornitermes cu-mulans Procornitermes spp., Globitermes sulfureus, Neocapritermes spp. e.g. N. opacus, N.
  • Odontotermes spp. Nasutitermes spp. e.g. N. corniger
  • Coptotermes spp. e.g. C. for-mosanus, C. gestroi, C. acinaciformis
  • Reticulitermes spp. e.g. R. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. virginicus
  • Cryptotermes spp. e.g. C. brevis, C. cavifrons
  • Pests from the class Chilopoda e.g. Geophilus spp., Scutigera spp. e.g. Scutigera coleoptrata
  • Pests from the class Diplopoda e.g. Blaniulus guttulatus, Julus spp., Narceus spp.
  • Pests from the class Symphyla e.g. Scutigerella immaculata, Insects from the order Dermaptera, e.g. Forficula auricularia, Insects from the order Collembola, e.g.
  • Onychiurus spp. e.g. Onychiurus armatus, Pests from the order Isopoda, e.g. Armadillidium vulgare, Oniscus asellus, Porcellio scaber, Insects from the order Phthiraptera, e.g. Damalinia spp., Pediculus spp. e.g. Pediculus hu-manus capitis, Pediculus humanus corporis, Pediculus humanus humanus; Pthirus pubis, Haematopinus spp. e.g. Haematopinus eurysternus, Haematopinus suis; Linognathus spp. e.g.
  • Further pest species which may be controlled by compounds I and its mixtures include: from the Phylum Mollusca, class Bivalvia, e.g., Dreissena spp.; class Gastropoda, e.g., Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, Succinea spp.; from the class of the helminths, e.g., Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp.,
  • the mixtures of the invention are particularly suitable for controlling the following causal agents of 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 (e.g. A. dauci or A. porri), oilseed rape (A. brassicicola or brassicae), sugar beets (A. tenuis), fruits (e.g. A. grandis), rice, soybeans, potatoes and tomatoes (e.g. A. solani, A. grandis or A. alternata), tomatoes (e.g. A. solani or A. alternata) and wheat (e.g. A. A.
  • C. ulmi Dutch elm disease
  • Cercospora spp. Cercospora leaf spots
  • corn e.g. Gray leaf spot: C. zeae-maydis
  • sugar beets e.g. C. beticola
  • sugar cane vegetables
  • coffee e.g. C. sojina or C. kikuchii
  • Cladobotryum syn. Dactylium
  • mycophilum (formerly Dactylium dendroides, teleomorph: Nectria albertinii, Nectria rosella syn. Hypomyces rosellus) on mushrooms; 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.
  • Corticium spp. e.g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans, cotton 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 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.
  • 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 oilseed 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 (f. sp. glycines now syn. F. virguliforme ) and F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans, and F.
  • F. graminearum or F. culmorum root rot, scab or head blight
  • F. oxysporum on tomatoes
  • F. solani f. sp. glycines now syn. F. virguliforme
  • F. tucumaniae and F. brasiliense each causing sudden death syndrome on
  • 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 bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e.g. G.
  • sabinae rust on pears
  • Helminthosporium spp. syn. Drechslera, teleomorph: Cochliobolus
  • Hemileia spp. e.g. H. vastatrix (coffee leaf rust) on coffee
  • Isariopsis clavispora syn. Cladosporium vitis
  • Macrophomina phaseolina syn. phaseoli
  • root and stem rot on soybeans and cotton
  • Microdochium syn. Fusarium
  • nivale pink snow mold
  • Microsphaera diffusa prowdery mildew
  • Monilinia spp. e.g. M. laxa, M. fructicola and M. fructigena (syn. Monilia spp.: 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: Zymoseptoria tritici formerly Septoria tritici: Septoria blotch) on wheat or M. fijiensis (syn.
  • Pseudocercospora fijiensis black Sigatoka disease
  • M. musicola on bananas M. arachidicola (syn. M. arachidis or Cercospora arachidis), M. berkeleyi on peanuts, M. pisi on peas and M. brassiciola on brassicas; Peronospora spp. (downy mildew) on cabbage (e.g. P. brassicae), oilseed 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 (syn. Leptosphaeria biglobosa and L. maculans: root and stem rot) on oilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off) on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn; Phomopsis spp. on sunflowers, vines (e.g.
  • P. 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
  • paprika and cucurbits e.g. P. capsici
  • soybeans e.g. P. megasperma, syn. P. sojae
  • potatoes and tomatoes e.g. P. infestans: late blight
  • broad-leaved trees e.g. P.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e.g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew
  • Polymyxa spp. e.g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P.
  • Pseudocercosporella herpotrichoides (syn. Oculimacula yallundae, O. acuformis: 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; Pyrenopeziza spp., e.g. P.
  • oligandrum on mushrooms Ramularia spp., e.g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley, R. areola (teleomorph: Mycosphaerella areola) on cotton and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, oilseed 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.
  • R. solani root and stem rot
  • Athelia rolfsii on soybeans, peanut, vegetables, corn, cereals and ornamentals; Septoria spp. on various plants, e.g. S. glycines (brown spot) on soybeans, S. tritici (syn. Zymoseptoria 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; Setosphaeria spp. (leaf blight) on corn (e.g.
  • nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum, syn. Septoria 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.
  • the compounds I and mixtures and compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases: rusts on soybean and cereals (e.g. Phakopsora pachyrhizi and P. meibomiae on soy; Puccinia tritici and P. striiformis on wheat); molds on specialty crops, soybean, oil seed rape and sunflowers (e.g. Botrytis cinerea on strawberries and vines, Sclerotinia sclerotiorum, S. minor and S.
  • Fusarium diseases on cereals e.g. Fusarium culmorum and F. graminearum on wheat
  • downy mildews on specialty crops e.g. Plasmopara viticola on vines, Phytophthora infestans on potatoes
  • powdery mildews on specialty crops and cereals e.g. Uncinula necator on vines, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals
  • leaf spots on cereals, soybean and corn e.g. Septoria tritici and S. nodorum on cereals, S. glycines on soybean, Cercospora spp. on corn and soybean).
  • test solutions are prepared as follow:
  • the active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water : acteone.
  • the test solution is prepared at the day of use.
  • Test solutions are prepared in general at concentrations of 1000 ppm, 500 ppm, 300 ppm, 100 ppm and 30 ppm (wt/vol).
  • Limonius spp. (genus of click beetles), Agriotes spp. (genus of lined click beetle), and other early-season soil pests of cereals
  • the test consisted of treated wheat seeds planted in a field in a randomized complete block design with four replications. The single compounds or mixture were applied to the seeds, and the seeds were planted into the field. A naturally-occurring population of early-season soil pests was utilized for the test. Plant stand reduction was visually assessed per treatment. The mixture had a surprisingly higher effect than expected, i.e., higher than the expected combined control effect of the mixture partners.
  • the active compounds are formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the stock solutions are mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • the test is performed as described for each pathogen below.
  • the plates are placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs are measured at 405 nm 7 days after the inoculation.
  • the measured parameters are compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages are converted into efficacies.
  • An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens are not growing.
  • the expected efficacies of active compound mixtures are determined using Colby's formula [R.S. Colby, “Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacies.
  • Test F Activity against the grey mold Botrytis cinerea in the microtiterplate test (BOTRCI) A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution is then added.
  • BOTRCI microtiterplate test
  • Test F Activity against rice blast Pyricularia oryzae in the microtiterplate test (PYRIOR) A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution is then added.
  • Test F3 Activity against leaf blotch on wheat caused by Septoria tritici (SEPTTR) A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution is then added.
  • SEPTTR Septoria tritici
  • Test F Activity against anthracnose caused by Colletotrichum orbiculare in the microtiterplate test (COLLLA) A spore suspension of Colletotrichum orbiculare in an aqueous bio malt solution is then added.
  • COLLLA microtiterplate test
  • Feeding suppression rate(%) (feeding rate in untreated plot - feeding rate in treated plot) ⁇ 100 / feeding rate in untreated plot
  • Spodoptera spp. / Spodoptera litura (common cutworm) Test Method In the single agents or mixtures at various concentrations was immersed a 7 cm diameter cabbage leaf disc for 30 seconds, the immersed leaf discs were air dried and placed in a plastic petri dish, five Spodoptera litura of 3rd instar were inoculated in each petri dish and then covered with a lid. 4 days after inoculation, the area percentage of the cabbage leaf discs eaten was surveyed, and the percentage of feeding damage suppression was calculated using the above formula (1).
  • Aphis spp. / Aphis gossypii (cotton aphid) Test Method: In the single agents or mixtures at various concentrations was immersed a 7 cm diameter cucumber leaf disc for 30 seconds, the immersed leaf discs were air dried and fixed with agar, 8 adult Aphis gossypii Glover were inoculated in each petri dish and then covered with a lid. 5 days after inoculation, the number of infesting Aphis gossypii on the cucumber leaf disc was counted, and the control value was calculated using the following formula (2).
  • T number of infestants after treating in the untreated group
  • C number of infestants after treating in the treated group.

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Abstract

Pesticidal mixtures comprising as active compounds A) an ethylsulfone compound I-1 and B) one or two or more further compounds II selected from a group of certain fungicides, insecticides and nematicides.

Description

PESTICIDAL MIXTURES COMPRISING AN ETHYLSULFONE COMPOUND
The invention relates to pesticidal mixtures comprising as active compounds an ethylsulfone compound and one or more further pesticides. The one or more further pesticide may be e.g. at least one nAChR competitive or allosteric modulator compound. Furthermore, the invention relates to methods of applying said mixtures.
The invention thus relates to pesticidal mixtures comprising as active compounds
A) the compound I which is selected from the compound I-1 of formula I-1:
and
B) at least one further compound II selected from the groups of:
Group F (fungicides): F.1:-Azoxystrobin, F.2:-Trifloxystrobin, F.3:-Picoxystrobin, F.4:-Pyraclostrobin, F.5:-Mandestrobin, F.66: fluoxastrobin, F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.9:-Bixafen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.15:-Fluindapyr, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-Isoflucypram, F.19:-Cyclobutrifluram, F.20:-Oxathiapiprolin, F.21:-Fluoxapiprolin, F.22:-Metalaxyl, F.23:-Metalaxyl-M, F.24:-Picarbutrazox, F.25:-Ethaboxam, F.26:-Dimethomorph, F.27:-Fluopicolide, F.28:-Cyproconazole, F.29:-Difenoconazole, F.30:-Prothioconazole, F.31:-Flutriafol, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.41:-Fluoxytioconazole, F.42:-Fludioxinil, F.43:-Thiabendazole, F.44:-Silthiofam, F.45:-Fluazinam, F.46:-Ziram, F.47:-Thiram, F.48:-Carbendazim, F.49:-Thiophanate-methyl, F.50:-Valifenalate, F.51:-Diclobenthiazox, F.52:-Tolclofos-methyl, F.53:-Hymexazol, F.54:-Flumetylsulforim, F.55:-Fenpicoxamide, F.56:-Florylpicoxamid, F.57:-Metarylpicoxamid, F.58:-Natamycin, F.59:-Mandipropamid, F.60:-Flutolanil, F.61:-Fenamidone, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil;
Group In (insecticides): In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.4: Dinotefuran, In.5: Thiacloprid, In.6: Acetamiprid, In.7: Sulfoxaflor, In.8: Flupyradifurone, In.9: Triflumezopyrim, In.10: Dicloromezotiaz , In.11: Fenmezoditiaz, In.12: Flupyrimin, In.13: Tefluthrin, In.14: Bifenthrin, In.15: Cypermethrin, In.16: alpha-Cypermethrin, In.17: zeta-Cypermethrin, In.18: lambda-Cyhalothrin, In.19: beta-Cyfluthrin, In.20: Thiodicarb, In.21: Methiocarb, In.22: Acephate, In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.25: Tetraniliprole, In.26: Cyclaniliprole, In.27: Fipronil, In.28: Isocycloseram, In.29: Fluxametamide, In.30: Broflanilide, In.31: Nicofluprole, In.32: Tigolaner, In.33: Dimpropyridaz, In.34: Spinosad, In.35: Spinetoram, In.36: Spirotetramat, In.37: Spiropidion, In.38: Spidoxamat, In.39: Abamectin, In.40: Afidopyropen, In.41: Tyclopyrazoflor, In.42: Tiapyrachlor, In.43: Indazapyroxamet, In.44: Indacyclometamide, In.45: Benzpyrimoxan, In.46: Flometoquin, In.47: Cyetpyrafen, In.48: Pyflubumide, In.49: Oxazosulfyl;
Group N (nematicides): N.1: Tioxazafen, N.2: Fluazaindolizine, N.3: Flufensulfone, N.4: Flupentiofenox, N.5: Sulfiflumin, Biopesticides: N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), N.9: B. thuringiensis EX297512, N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.16: Bacillus amyloliquefaciens velezensis MBI600;
wherein component A and component B are present in a weight ratio of from 1000:1 to 1:1000.
In.20: Thiodicarb and In.39:Abamectin are insecticides, but belong at the same time to group N (nematicides). F.10: Fluopyram and F.19: Cyclobutrifluram are fungicides, but belong at the same time to group N (nematicides).
The mentioned mixtures are mixtures of compound I and II in a synergistically effective amount.
One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control. Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests.
Another difficulty in relation to the use of pesticides is that the repeated and exclusive application of an individual pesticidal compound leads in many cases to a rapid selection of pests which have developed natural or adapted resistance against the active compound in question. Therefore, there is a need for pest control agents that help prevent or overcome resistance.

WO2017146226 describes the ethylsulfone compound of formula I-1, which is mentioned to be useful for combating invertebrate pests.
It is an object of the invention to provide pesticidal mixtures and/or compounds which solves at least one of the discussed problems as reducing the dosage rate, enhancing the spectrum of activity or combining knock-down activity with prolonged control or as to resistance management.
It has been found that at least one of these objectives is achieved by the combination of active compounds defined in the outset.
Moreover, it has also been found that simultaneous, that is joint or separate, application of an active compound I and one or more active compounds B or successive application of an active compound I and one or more active compounds B allows enhanced control of pests compared to the control rates that are possible with the individual compounds.
Moreover, the invention relates to
- a composition comprising the pesticidal mixture as defined herein and at least one inert　 liquid and/or solid acceptable carrier;
- an agricultural composition comprising the pesticidal mixture as defined herein and at　 least one inert liquid and/or solid acceptable carrier;
- a method for controlling or combating invertebrate pests or harmful pathogenic fungi, comprising contacting said pest or its food supply, habitat, breeding grounds with a pesticidally effective amount of the pesticidal mixture as defined herein;
- a method of protecting plants from attack or infestation by invertebrate pests or harmful pathogenic fungi, contacting a plant, a plant propagation material or soil or water in which the plant is growing, with a pesticidally effective amount of the pesticidal mixture as defined herein;
- a plant propagation material comprising the pesticidal mixture as defined herein in an amount of from 0.1 g to 10 kg per 100 kg of seed;
- a method for protection of plant propagation material comprising contacting the plant propagation material with the pesticidal mixture as defined herein in an amount of from 0.1 g to 10 kg per 100 kg of plant propagation material;
- the use of the pesticidal mixture as defined herein for protecting growing plants or plant propagation material from attack or infestation by invertebrate pests or harmful pathogenic fungi;
- a method for controlling phytopathogenic harmful fungi, wherein the fungi, their habitat or the plants to be protected against fungal attack, the soil or seed are treated with an effective amount of the pesticidal mixture comprising compound I as defined herein and at least one specific compound II as defined herein;
- a method for protecting plants from phytopathogenic harmful fungi, wherein the fungi, their habitat or the plants to be protected against fungal attack, the soil or seed are treated with an effective amount of the pesticidal mixture comprising compound I as defined herein and at least one specific compound II as defined herein.
The mixtures according to the invention may be a physical mixture of the compound I and the at least one compound II. Accordingly, the invention also provides a mixture comprising compound I and at least one compound II. However, the composition may also be any combination of compound I with at least one compound II, it not being required for compounds A and B to be present together in the same formulation.
An example of a composition according to the invention or to be used according to the invention in which the compound I and the at least one compound II are not present together in the same formulation is a combipack. In a combipack, two or more components of a combipack are packaged separately, i.e., not jointly pre-formulated. As such, combipacks include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition. One example is a two-component combipack. Accordingly, the invention also relates to a two-component combipack, comprising a first component which in turn comprises a compound I, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary, and a second component which in turn comprises at least one compound II, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary. More details, e.g. as to suitable liquid and solid carriers, surfactants and customary auxiliaries are described below.
The "combined" use of compound I "in combination with" at least one compound II on the one hand can be understood as using a physical mixture of compound I and at least one compound II. On the other hand, the combined use may also consist in using the compound I and the at least one compound II separately, but within a sufficiently short time of one another so that the desired effect can take place. More detailed illustrations of the combined use can be found in the specifications below.
The term "invertebrate pest" (also referred to as animal pests) as used herein encompasses animal populations, such as insects, arachnids and nematodes, which may attack plants, thereby causing substantial damage to the plants attacked, as well as ectoparasites which may infest animals, in particular warm-blooded animals such as e.g. mammals or birds, or other higher animals such as reptiles, amphibians or fish, thereby causing substantial damage to the animals infested.
The term "compound according to the invention", or "compound of formula I" or "compound I" comprises the compound as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof. The term "compound of the invention" is to be understood as equivalent to the term "compound according to the invention", therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof. The same applies to the mixtures of the invention, which are understood to be mixtures of the compounds according to the invention.
The term "stereoisomers" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
The compound of formula I-1 has a stereocenter and thus exists in enantiomers (stereoisomers). In the mixtures according to the invention, the compound of formula I-1 is used either as a mixture of the two enantiomers, as a racemate (1:1 mixture of the two enantiomers) or as a pure enantiomer (R- or S-enantiomer).
The compounds of the invention may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities. The invention includes both amorphous and crystalline compounds of the formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula I are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound I has a basic functionality or by reacting an acidic compound I with a suitable base.
Suitable agriculturally acceptable salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4 +) and substituted ammonium in which one to four of the hydrogen atoms are replaced by C1-C4-alkyl, C1-C4-hydroxyalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl-triethylammonium, 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, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, 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 formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
The commercially available further compounds B may be found in The Pesticide Manual, 18th Edition, British Crop Protection Council (2018) among other publications, and its online database https://www.bcpc.org/product/bcpc-online-pesticide-manual-latest-version, or may be obtained via literature-known processes.
The biopesticides in group N are commercially available or may be obtained from the following sources:
N.6: Pasteuria nishizawae (Clariva): Pasteuria nishizawae Pn1 isolated from a soybean field in the mid-2000s in Illinois, U.S.A. (ATCC SD 5833; Federal Register 76(22), 5808, February 2, 2011; e.g. Clariva (trademark) PN from Syngenta Crop Protection, LLC, USA).
N.7: Burkholderia rinojensis A 396: Burkholderia sp. A396 isolated from soil in Nikko, Japan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc., USA).
N.8: Bacillus firmus I1582 (VOTIVO): B. firmus CNCM I-1582, a variant of parental strain EIP-N1 (CNCM I-1556) isolated from soil of central plain area of Israel (WO 2009/126473, US6,406,690; e.g. Votivo (trademark registered) from Bayer CropScience LP, USA).
N.16: Bacillus amyloliquefaciens velezensis MBI600: B. a. ssp. plantarum or B. vele-zensis MBI600 isolated from faba bean in Sutton Bonington, Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRL B 50595; US 2012/0149571 A1; e.g. Integral (trademark registered)from BASF Corp., USA).
According to the invention, the solid material (dry matter) of the biopesticides (with the ex-ception of oils e.g. Neem oil) are considered as active components (e.g. to be obtained after drying or evaporation of the extraction or suspension medium in case of liquid formulations of the microbial pesticides).
In accordance with the invention, the weight ratios and percentages used herein for a biological extract e.g. Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).
The total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including dormant forms, can be determined using the amount of CFU of the respective microorganism to calculate the total weight of the respective active component with the following equation that 1x1010 CFU equals one gram of total weight of the respective active component. Colony forming unit is measure of viable microbial cells, in particular fungal and bacterial cells. In addition, here “CFU” may also be understood as the number of (juvenile) individual nematodes in case of (entomo-pathogenic) nematode biopesticides, e.g. Steinernema feltiae.
When mixtures comprising microbial pesticides are employed in crop protection, the application rates range from 1x106 to 5x1016 (or more) CFU/ha, preferably from 1x108 to 1x1013 CFU/ha, and even more preferably from 1x109 to 5x1015 CFU/ha and in particular from 1x1012 to 5x1014 CFU/ha. In the case of nematodes as microbial pesticides (e.g. Steinernema feltiae), the application rates regularly range from 1x105 to 1x1012 (or more), preferably from 1x108 to 1x1011, more preferably from 5x108 to 1x1010 individuals (e.g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha.
When mixtures comprising microbial pesticides are employed in seed treatment, the application rates generally range from 1x106 to 1x1012 (or more) CFU/seed, preferably from 1x106 to 1x109 CFU/seed. Furthermore, the application rates with respect to seed treatment generally range from 1x107 to 1x1014 (or more) CFU per 100 kg of seed, preferably from 1x109 to 1x1012 CFU per 100 kg of seed.
We have found that simultaneous, that is joint or separate, application of the compound I and at least one compound II or successive application of the compounds of formula I and at least one compound II allows better control of animal pests than is possible with the individual compounds alone (synergistic mixtures).
The compound I can be used as synergists for certain insecticidal and fungicidal active compounds. By simultaneous, that is joint or separate, application of the compound I with at least one active compound II, the insecticidal or fungicidal activity is increased in a superadditive manner.
Preferred embodiments of the invention relate to pesticidal mixtures wherein component A and component B are present in a total weight ratio of from 1000:1 to 1:1000, 500:1 to 1:500, 250:1 to 1:250, 100:1 to 1:100, 50:1 to 1:50, or 10:1 to 1:10.
Other preferred embodiment of the invention relates to pesticidal mixtures wherein component A and component B are present in a total weight ratio of from 20:1 to 1:500, preferably 10:1 to 1:100, more preferably 10:1 to 1:50, more preferably 10:1 to 1:25, particularly 10:1 to 1:10.
In one embodiment (E-1), the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from F.1:-Azoxystrobin, F.2:-Trifloxystrobin, F.3:-Picoxystrobin, F.4:-Pyraclostrobin, F.5:-Mandestrobin, F.66: fluoxastrobin, F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-Isoflucypram, F.19:-Cyclobutrifluram, F.20:-Oxathiapiprolin, F.21:-Fluoxapiprolin, F.22:-Metalaxyl, F.23:-Metalaxyl-M, F.24:-Picarbutrazox, F.25:-Ethaboxam, F.29:-Difenoconazole, F.30:-Prothioconazole, F.31:-Flutriafol, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.41:-Fluoxytioconazole, F.42:-Fludioxinil, F.43:-Thiabendazole, F.45:-Fluazinam, F.47:-Thiram, F.49:-Thiophanate-methyl, F.58:-Natamycin, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil;
In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.4: Dinotefuran, In.6: Acetamiprid, In.8: Flupyradifurone, In.12: Flupyrimin, In.13: Tefluthrin, In.14: Bifenthrin, In.19: beta-Cyfluthrin, In.20: Thiodicarb, In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.25: Tetraniliprole, In.26: Cyclaniliprole, In.27: Fipronil, In.28: Isocycloseram, In.30: Broflanilide, In.31: Nicofluprole, In.32: Tigolaner, In.33: Dimpropyridaz, In.39: Abamectin, In.49: Oxazosulfyl;
N.1: Tioxazafen, N.2: Fluazaindolizine, N.3: Flufensulfone, N.4: Flupentiofenox, N.5: Sulfiflumin, N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), F.10 Fluopyram + N.8, N.9: B. thuringiensis EX297512, N.8: + N.9 (VOTIVO 2.0), N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.11: + N.12 (Presence/Avodigen), N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.13 + N.7 + N.14 + N.15 (BSST), N.16: Bacillus amyloliquefaciens velezensis MBI600, N.16 + cis-jasmone.
In another embodiment (E-2), the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from F.4:-Pyraclostrobin, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.22:-Metalaxyl, F.31:-Flutriafol, F.35:-Mefentrifluconazole, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.42:-Fludioxinil, F.43:-Thiabendazole, F.45:-Fluazinam, F.49:-Thiophanate-methyl, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil; In.1: Clothianidin, In.2: Thiamethoxam, In.4: Dinotefuran, In.6: Acetamiprid, In.20: Thiodicarb, In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.27: Fipronil, In.39: Abamectin, Bacillus species: N.12: Bacillus subtilis FMCH002.
In one embodiment (Embodiment E-F), the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from F.1:-Azoxystrobin, F.2:-Trifloxystrobin, F.3:-Picoxystrobin, F.4:-Pyraclostrobin, F.5:-Mandestrobin, F.66: fluoxastrobin, F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.9:-Bixafen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.15:-Fluindapyr, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-Isoflucypram, F.19:-Cyclobutrifluram, F.20:-Oxathiapiprolin, F.21:-Fluoxapiprolin, F.22:-Metalaxyl, F.23:-Metalaxyl-M, F.24:-Picarbutrazox, F.25:-Ethaboxam, F.26:-Dimethomorph, F.27:-Fluopicolide, F.28:-Cyproconazole, F.29:-Difenoconazole, F.30:-Prothioconazole, F.31:-Flutriafol, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.41:-Fluoxytioconazole, F.42:-Fludioxinil, F.43:-Thiabendazole, F.44:-Silthiofam, F.45:-Fluazinam, F.46:-Ziram, F.47:-Thiram, F.48:-Carbendazim, F.49:-Thiophanate-methyl, F.50:-Valifenalate, F.51:-Diclobenthiazox, F.52:-Tolclofos-methyl, F.53:-Hymexazol, F.54:-Flumetylsulforim, F.55:-Fenpicoxamide, F.56:-Florylpicoxamid, F.57:-Metarylpicoxamid, F.58:-Natamycin, F.59:-Mandipropamid, F.60:-Flutolanil, F.61:-Fenamidone, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil.
In particular, the invention relates to mixtures of compound formula I-1 with a component B selected from fungicides F.1:-Azoxystrobin, F.2:-Trifloxystrobin, F.3:-Picoxystrobin, F.4:-Pyraclostrobin, F.5:-Mandestrobin, F.66: fluoxastrobin, F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-Isoflucypram, F.19:-Cyclobutrifluram, F.20:-Oxathiapiprolin, F.21:-Fluoxapiprolin, F.22:-Metalaxyl, F.23:-Metalaxyl-M, F.24:-Picarbutrazox, F.25:-Ethaboxam, F.29:-Difenoconazole, F.30:-Prothioconazole, F.31:-Flutriafol, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.41:-Fluoxytioconazole, F.42:-Fludioxinil, F.43:-Thiabendazole, F.45:-Fluazinam, F.47:-Thiram, F.49:-Thiophanate-methyl, F.58:-Natamycin, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil.
In another embodiment, the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from F.4:-Pyraclostrobin, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.22:-Metalaxyl, F.31:-Flutriafol, F.35:-Mefentrifluconazole, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.42:-Fludioxinil, F.43:-Thiabendazole, F.45:-Fluazinam, F.49:-Thiophanate-methyl, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil.
In one embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from the strobilurins F.1:-Azoxystrobin, F.2:-Trifloxystrobin, F.3:-Picoxystrobin, F.4:-Pyraclostrobin, F.5:-Mandestrobin, F.66: fluoxastrobin.
In one embodiement, the invention relates to mixtures of compound formula I-1 with a component B selected from the SDHI inhibitors F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-Isoflucypram, F.19:-Cyclobutrifluram.
In one embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from oomycetes fungicides F.20:-Oxathiapiprolin, F.21:-Fluoxapiprolin, F.22:-Metalaxyl, F.23:-Metalaxyl-M, F.24:-Picarbutrazox, F.25:-Ethaboxam.
In one embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from the DMI fungicides (azoles) F.29:-Difenoconazole, F.30:-Prothioconazole, F.31:-Flutriafol, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.41:-Fluoxytioconazole. More particularly, the invention relates to mixtures of of compound formula I-1 with a component B selected from the DMI fungicides (azoles) F.29:-Difenoconazole, F.30:-Prothioconazole, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.39:-Triticonazole, F.41:-Fluoxytioconazole.
In one embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from the fungicides F.42:-Fludioxinil, F.43:-Thiabendazole, F.45:-Fluazinam, F.47:-Thiram, F.49:-Thiophanate-methyl, F.58:-Natamycin, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil.
In one embodiment (Embodiment E-In), the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from insecticides In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.4: Dinotefuran, In.5: Thiacloprid, In.6: Acetamiprid, In.7: Sulfoxaflor, In.8: Flupyradifurone, In.9: Triflumezopyrim, In.10: Dicloromezotiaz , In.11: Fenmezoditiaz, In.12: Flupyrimin, In.13: Tefluthrin, In.14: Bifenthrin, In.15: Cypermethrin, In.16: alpha-Cypermethrin, In.17: zeta-Cypermethrin, In.18: lambda-Cyhalothrin, In.19: beta-Cyfluthrin, In.20: Thiodicarb, In.21: Methiocarb, In.22: Acephate, In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.25: Tetraniliprole, In.26: Cyclaniliprole, In.27: Fipronil, In.28: Isocycloseram, In.29: Fluxametamide, In.30: Broflanilide, In.31: Nicofluprole, In.32: Tigolaner, In.33: Dimpropyridaz, In.34: Spinosad, In.35: Spinetoram, In.36: Spirotetramat, In.37: Spiropidion, In.38: Spidoxamat, In.39: Abamectin, In.40: Afidopyropen, In.41: Tyclopyrazoflor, In.42: Tiapyrachlor, In.43: Indazapyroxamet, In.44: Indacyclometamide, In.45: Benzpyrimoxan, In.46: Flometoquin, In.47: Cyetpyrafen, In.48: Pyflubumide, In.49: Oxazosulfyl.
In particular, the invention relates to mixtures of compound formula I-1 with a component B selected from insecticides In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.4: Dinotefuran, In.6: Acetamiprid, In.8: Flupyradifurone, In.12: Flupyrimin, In.13: Tefluthrin, In.14: Bifenthrin, In.19: beta-Cyfluthrin, In.20: Thiodicarb, In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.25: Tetraniliprole, In.26: Cyclaniliprole, In.27: Fipronil, In.28: Isocycloseram, In.30: Broflanilide, In.31: Nicofluprole, In.32: Tigolaner, In.33: Dimpropyridaz, In.39: Abamectin, In.49: Oxazosulfyl.
In another embodiment (E-2), the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from In.1: Clothianidin, In.2: Thiamethoxam, In.4: Dinotefuran, In.6: Acetamiprid, In.20: Thiodicarb, In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.27: Fipronil, In.39: Abamectin.
In one embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from the insecticides In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.4: Dinotefuran, In.6: Acetamiprid, In.8: Flupyradifurone, In.12: Flupyrimin, in particular In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.6: Acetamiprid.
In one embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from the pyrethroids In.13: Tefluthrin, In.14: Bifenthrin, In.19: beta-Cyfluthrin.
In one embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from the diamides In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.25: Tetraniliprole, In.26: Cyclaniliprole.
In one embodiment, the invention relates to mixtures of compound formula I-1 with a component B which is In.27: Fipronil.
In one embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from the insecticides In.28: Isocycloseram and In.30: Broflanilide.
In one embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from the insecticides In.20: Thiodicarb, In.31: Nicofluprole, In.32: Tigolaner, In.33: Dimpropyridaz, In.39: Abamectin, In.49: Oxazosulfyl.
In one embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from the insecticides clothianidin, broflanilide, chlorantraniliprole, fipronil; preferably clothianidin.
In one embodiment (Embodiment E-N), the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from nematicides In.20: Thiodicarb, In.39: Abamectin, F.10: Fluopyram, F.19: Cyclobutrifluram, N.1: Tioxazafen, N.2: Fluazaindolizine, N.3: Flufensulfone, N.4: Flupentiofenox, N.5: Sulfiflumin, Biopesticides: N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), N.9: B. thuringiensis EX297512, N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.16: Bacillus amyloliquefaciens velezensis MBI600.
In particular, the invention relates to mixtures of compound formula I-1 with a component B selected from nematicides In.20: Thiodicarb, In.39: Abamectin, F.10: Fluopyram, F.19: Cyclobutrifluram, N.1: Tioxazafen, N.5: Sulfiflumin, N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), N.9: B. thuringiensis EX297512, N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.16: Bacillus amyloliquefaciens velezensis MBI600.
In another embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from nematicides, N.1: Tioxazafen, N.2: Fluazaindolizine, N.3: Flufensulfone, N.4: Flupentiofenox, N.5: Sulfiflumin, N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), F.10 Fluopyram + N.8, N.9: B. thuringiensis EX297512, N.8: + N.9 (VOTIVO 2.0), N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.11: + N.12 (Presence/Avodigen), N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.13 + N.7 + N.14 + N.15 (BSST), N.16: Bacillus amyloliquefaciens velezensis MBI600, N.16 + cis-jasmone.
In another embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from nematicides N.1: Tioxazafen, N.2: Fluazaindolizine, N.3: Flufensulfone, N.4: Flupentiofenox, N.5: Sulfiflumin.
In another embodiment, the invention relates to mixtures of compound formula I-1 with a component B selected from nematicides N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), N.9: B. thuringiensis EX297512, N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.16: Bacillus amyloliquefaciens velezensis MBI600.
In particular, the invention relates to mixtures of compound formula I-1 with a component B selected from biopesticides N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), F.10 Fluopyram + N.8, N.9: B. thuringiensis EX297512, N.8: + N.9 (VOTIVO 2.0), N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.11: + N.12 (Presence/Avodigen), N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.13 + N.7 + N.14 + N.15 (BSST), N.16: Bacillus amyloliquefaciens velezensis MBI600, N.16 + cis-jasmone.
In another embodiment, the mixtures of the invention are mixtures of the compound of formula I-1 with a component B) selected from Bacillus species, in particular Bacillus subtilis, more particular Bacillus subtilis FMCH002.
In particular, the mixture of the invention is one of the mixtures selected from mixtures M-1 to M-135:
In one aspect, the invention relates to a mixture of compound I-1 with F.1 (mixture M-1).
In one aspect, the invention relates to a mixture of compound I-1 with F.2 (mixture M-2).
In one aspect, the invention relates to a mixture of compound I-1 with F.3 (mixture M-3).
In one aspect, the invention relates to a mixture of compound I-1 with F.4 (mixture M-4).
In one aspect, the invention relates to a mixture of compound I-1 with F.5 (mixture M-5).
In one aspect, the invention relates to a mixture of compound I-1 with F.6 (mixture M-6).
In one aspect, the invention relates to a mixture of compound I-1 with F.7 (mixture M-7).
In one aspect, the invention relates to a mixture of compound I-1 with F.8 (mixture M-8).
In one aspect, the invention relates to a mixture of compound I-1 with F.9 (mixture M-9).
In one aspect, the invention relates to a mixture of compound I-1 with F.10 (mixture M-10).
In one aspect, the invention relates to a mixture of compound I-1 with F.11 (mixture M-11).
In one aspect, the invention relates to a mixture of compound I-1 with F.12 (mixture M-12).
In one aspect, the invention relates to a mixture of compound I-1 with F.13 (mixture M-13).
In one aspect, the invention relates to a mixture of compound I-1 with F.14 (mixture M-14).
In one aspect, the invention relates to a mixture of compound I-1 with F.15 (mixture M-15).
In one aspect, the invention relates to a mixture of compound I-1 with F.16 (mixture M-16).
In one aspect, the invention relates to a mixture of compound I-1 with F.17 (mixture M-17).
In one aspect, the invention relates to a mixture of compound I-1 with F.18 (mixture M-18).
In one aspect, the invention relates to a mixture of compound I-1 with F.19 (mixture M-19).
In one aspect, the invention relates to a mixture of compound I-1 with F.20 (mixture M-20).
In one aspect, the invention relates to a mixture of compound I-1 with F.21 (mixture M-21).
In one aspect, the invention relates to a mixture of compound I-1 with F.22 (mixture M-22).
In one aspect, the invention relates to a mixture of compound I-1 with F.23 (mixture M-23).
In one aspect, the invention relates to a mixture of compound I-1 with F.24 (mixture M-24).
In one aspect, the invention relates to a mixture of compound I-1 with F.25 (mixture M-25).
In one aspect, the invention relates to a mixture of compound I-1 with F.26 (mixture M-26).
In one aspect, the invention relates to a mixture of compound I-1 with F.27 (mixture M-27).
In one aspect, the invention relates to a mixture of compound I-1 with F.28 (mixture M-28).
In one aspect, the invention relates to a mixture of compound I-1 with F.29 (mixture M-29).
In one aspect, the invention relates to a mixture of compound I-1 with F.30 (mixture M-30).
In one aspect, the invention relates to a mixture of compound I-1 with F.31 (mixture M-31).
In one aspect, the invention relates to a mixture of compound I-1 with F.32 (mixture M-32).
In one aspect, the invention relates to a mixture of compound I-1 with F.33 (mixture M-33).
In one aspect, the invention relates to a mixture of compound I-1 with F.34 (mixture M-34).
In one aspect, the invention relates to a mixture of compound I-1 with F.35 (mixture M-35).
In one aspect, the invention relates to a mixture of compound I-1 with F.36 (mixture M-36).
In one aspect, the invention relates to a mixture of compound I-1 with F.37 (mixture M-37).
In one aspect, the invention relates to a mixture of compound I-1 with F.38 (mixture M-38).
In one aspect, the invention relates to a mixture of compound I-1 with F.39 (mixture M-39).
In one aspect, the invention relates to a mixture of compound I-1 with F.40 (mixture M-40).
In one aspect, the invention relates to a mixture of compound I-1 with F.41 (mixture M-41).
In one aspect, the invention relates to a mixture of compound I-1 with F.42 (mixture M-42).
In one aspect, the invention relates to a mixture of compound I-1 with F.43 (mixture M-43).
In one aspect, the invention relates to a mixture of compound I-1 with F.44 (mixture M-44).
In one aspect, the invention relates to a mixture of compound I-1 with F.45 (mixture M-45).
In one aspect, the invention relates to a mixture of compound I-1 with F.46 (mixture M-46).
In one aspect, the invention relates to a mixture of compound I-1 with F.47 (mixture M-47).
In one aspect, the invention relates to a mixture of compound I-1 with F.48 (mixture M-48).
In one aspect, the invention relates to a mixture of compound I-1 with F.49 (mixture M-49).
In one aspect, the invention relates to a mixture of compound I-1 with F.50 (mixture M-50).
In one aspect, the invention relates to a mixture of compound I-1 with F.51 (mixture M-51).
In one aspect, the invention relates to a mixture of compound I-1 with F.52 (mixture M-52).
In one aspect, the invention relates to a mixture of compound I-1 with F.53 (mixture M-53).
In one aspect, the invention relates to a mixture of compound I-1 with F.54 (mixture M-54).
In one aspect, the invention relates to a mixture of compound I-1 with F.55 (mixture M-55).
In one aspect, the invention relates to a mixture of compound I-1 with F.56 (mixture M-56).
In one aspect, the invention relates to a mixture of compound I-1 with F.57 (mixture M-57).
In one aspect, the invention relates to a mixture of compound I-1 with F.58 (mixture M-58).
In one aspect, the invention relates to a mixture of compound I-1 with F.59 (mixture M-59).
In one aspect, the invention relates to a mixture of compound I-1 with F.60 (mixture M-60).
In one aspect, the invention relates to a mixture of compound I-1 with F.61 (mixture M-61).
In one aspect, the invention relates to a mixture of compound I-1 with F.62 (mixture M-62).
In one aspect, the invention relates to a mixture of compound I-1 with F.63 (mixture M-63).
In one aspect, the invention relates to a mixture of compound I-1 with F.64 (mixture M-64).
In one aspect, the invention relates to a mixture of compound I-1 with F.65 (mixture M-65).
In one aspect, the invention relates to a mixture of compound I-1 with In.1 (mixture M-66).
In one aspect, the invention relates to a mixture of compound I-1 with In.2 (mixture M-67).
In one aspect, the invention relates to a mixture of compound I-1 with In.3 (mixture M-68).
In one aspect, the invention relates to a mixture of compound I-1 with In.4 (mixture M-69).
In one aspect, the invention relates to a mixture of compound I-1 with In.5 (mixture M-70).
In one aspect, the invention relates to a mixture of compound I-1 with In.6 (mixture M-71).
In one aspect, the invention relates to a mixture of compound I-1 with In.7 (mixture M-72).
In one aspect, the invention relates to a mixture of compound I-1 with In.8 (mixture M-73).
In one aspect, the invention relates to a mixture of compound I-1 with In.9 (mixture M-74).
In one aspect, the invention relates to a mixture of compound I-1 with In.10 (mixture M-75).
In one aspect, the invention relates to a mixture of compound I-1 with In.11 (mixture M-76).
In one aspect, the invention relates to a mixture of compound I-1 with In.12 (mixture M-77).
In one aspect, the invention relates to a mixture of compound I-1 with In.13 (mixture M-78).
In one aspect, the invention relates to a mixture of compound I-1 with In.14 (mixture M-79).
In one aspect, the invention relates to a mixture of compound I-1 with In.15 (mixture M-80).
In one aspect, the invention relates to a mixture of compound I-1 with In.16 (mixture M-81).
In one aspect, the invention relates to a mixture of compound I-1 with In.17 (mixture M-82).
In one aspect, the invention relates to a mixture of compound I-1 with In.18 (mixture M-83).
In one aspect, the invention relates to a mixture of compound I-1 with In.19 (mixture M-84).
In one aspect, the invention relates to a mixture of compound I-1 with In.20 (mixture M-85).
In one aspect, the invention relates to a mixture of compound I-1 with In.21 (mixture M-86).
In one aspect, the invention relates to a mixture of compound I-1 with In.22 (mixture M-87).
In one aspect, the invention relates to a mixture of compound I-1 with In.23 (mixture M-88).
In one aspect, the invention relates to a mixture of compound I-1 with In.24 (mixture M-89).
In one aspect, the invention relates to a mixture of compound I-1 with In.25 (mixture M-90).
In one aspect, the invention relates to a mixture of compound I-1 with In.26 (mixture M-91).
In one aspect, the invention relates to a mixture of compound I-1 with In.27 (mixture M-92).
In one aspect, the invention relates to a mixture of compound I-1 with In.28 (mixture M-93).
In one aspect, the invention relates to a mixture of compound I-1 with In.29 (mixture M-94).
In one aspect, the invention relates to a mixture of compound I-1 with In.30 (mixture M-95).
In one aspect, the invention relates to a mixture of compound I-1 with In.31 (mixture M-96).
In one aspect, the invention relates to a mixture of compound I-1 with In.32 (mixture M-97).
In one aspect, the invention relates to a mixture of compound I-1 with In.33 (mixture M-98).
In one aspect, the invention relates to a mixture of compound I-1 with In.34 (mixture M-99).
In one aspect, the invention relates to a mixture of compound I-1 with In.35 (mixture M-100).
In one aspect, the invention relates to a mixture of compound I-1 with In.36 (mixture M-101).
In one aspect, the invention relates to a mixture of compound I-1 with In.37 (mixture M-102).
In one aspect, the invention relates to a mixture of compound I-1 with In.38 (mixture M-103).
In one aspect, the invention relates to a mixture of compound I-1 with In.39 (mixture M-104).
In one aspect, the invention relates to a mixture of compound I-1 with In.40 (mixture M-105).
In one aspect, the invention relates to a mixture of compound I-1 with In.41 (mixture M-106).
In one aspect, the invention relates to a mixture of compound I-1 with In.42 (mixture M-107).
In one aspect, the invention relates to a mixture of compound I-1 with In.43 (mixture M-108).
In one aspect, the invention relates to a mixture of compound I-1 with In.44 (mixture M-109).
In one aspect, the invention relates to a mixture of compound I-1 with In.45 (mixture M-110).
In one aspect, the invention relates to a mixture of compound I-1 with In.46 (mixture M-111).
In one aspect, the invention relates to a mixture of compound I-1 with In.47 (mixture M-112).
In one aspect, the invention relates to a mixture of compound I-1 with In.48 (mixture M-113).
In one aspect, the invention relates to a mixture of compound I-1 with In.49 (mixture M-114).
In one aspect, the invention relates to a mixture of compound I-1 with N.1 (mixture M-115).
In one aspect, the invention relates to a mixture of compound I-1 with N.2 (mixture M-116).
In one aspect, the invention relates to a mixture of compound I-1 with N.3 (mixture M-117).
In one aspect, the invention relates to a mixture of compound I-1 with N.4 (mixture M-118).
In one aspect, the invention relates to a mixture of compound I-1 with N.5 (mixture M-119).
In one aspect, the invention relates to a mixture of compound I-1 with N.6 (mixture M-120).
In one aspect, the invention relates to a mixture of compound I-1 with N.7 (mixture M-121).
In one aspect, the invention relates to a mixture of compound I-1 with N.8 (mixture M-122).
In one aspect, the invention relates to a mixture of compound I-1 with F.10. + N.8 (mixture M-123).
In one aspect, the invention relates to a mixture of compound I-1 with N.9 (mixture M-124).
In one aspect, the invention relates to a mixture of compound I-1 with N.8: + N.9 (mixture M-125).
In one aspect, the invention relates to a mixture of compound I-1 with N.10 (mixture M-126).
In one aspect, the invention relates to a mixture of compound I-1 with N.11 (mixture M-127).
In one aspect, the invention relates to a mixture of compound I-1 with N.12 (mixture M-128).
In one aspect, the invention relates to a mixture of compound I-1 with N.11: + N.12 (mixture M-129).
In one aspect, the invention relates to a mixture of compound I-1 with N.13 (mixture M-130).
In one aspect, the invention relates to a mixture of compound I-1 with N.14 (mixture M-131).
In one aspect, the invention relates to a mixture of compound I-1 with N.15 (mixture M-132).
In one aspect, the invention relates to a mixture of compound I-1 with N.13 + N.7 + N.14 + N.15 (mixture M-133).
In one aspect, the invention relates to a mixture of compound I-1 with N.16 (mixture M-134).
In one aspect, the invention relates to a mixture of compound I-1 with N.16 + cis-jasmone (mixture M-135).
In one aspect, the invention relates to a mixture of compound I-1 with F.66: fluoxastrobin (mixture M-136).
In one embodiment of the invention, the mixtures of the invention are binary mixtures of the compound I and a compound II.
In another embodiment of the invention, the mixtures of the invention are mixtures comprising at least one further pesticide, i.e. higher mixtures. Preferably, the further pesticides are selected from the group as given for component B herein, with the proviso that no two of of the pesticides are identical. If there are more than two pesticides present in a mixture according to the invention, the weight ratio of each of the components to the other components is in the ratio ranges as given for the ratios of two pesticides, i.e. from 1000:1 to 1:1000, 500:1 to 1:500, 250:1 to 1:250, 100:1 to 1:100, 50:1 to 1:50, or 10:1 to 1:10; or 20:1 to 1:500, or 10:1 to 1:100, or 10:1 to 1:50, or 10:1 to 1:25.
In a further embodiment of the invention, the mixtures of the invention are mixtures of I-1 (component A) and a compound II (component B) and a further compound II (component C), wherein the component C is selected from the same group of compounds as component B, with the proviso that component B and C are not identical. These mixtures comprise at least three active compounds. In one embodiment, the mixtures of the invention consist of three active compounds (A, B, C), i.e. three-way mixtures.In another embodiment, the mixtures of the invention may comprise further active compounds beyond these three components.
The pesticides B and C, with which compound I-1 are mixed, may be two fungicides, or an insecticide and a fungicide, or an insecticide and a nematicide.
In particular, the following mixtures of Table T are part of the invention:
In another embodiment of the invention, the mixtures of the invention are mixtures of I-1 and a further compound, comprising two further pesticides, i.e. four-way mixtures.
In a special embodiment of the invention, the mixtures of the invention are mixtures of I-1 with a compound II (component B), which comprise two further compounds II (component C and D), wherein the the components C and D are selected from the same group of compounds as component B, with the proviso that none of components B, C and D are identical.
In particular, the mixtures of the invention are mixtures of each three-way mixture of Table T above, which further comprise one of the pesticides as given for component B.
In another embodiment of the invention, the mixtures of the invention are mixtures comprising three further pesticides, i.e. five-way mixtures. In particular, the mixtures of the invention are mixtures of each three-way mixture of Table T above, which further comprise two of the pesticides as given in the list for component B.
The invention also relates to agrochemical compositions comprising an auxiliary and a mixture of the invention.
An agrochemical composition comprises a pesticidally effective amount of a mixture of the invention.
The compound I and its mixtures can be converted into customary types of agro-chemical 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 e.g. 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, e.g. 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. Suitable solid carriers or fillers are mineral earths.
Suitable surfactants are surface-active compounds, e.g. anionic, cationic, nonionic, and amphoteric surfactants, block polymers, polyelectrolytes. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International or North American Ed.). Suitable anionic surfactants are alkali, alkaline earth, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates. Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants. Suitable cationic surfactants are qua-ternary surfactants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably 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%.
Various types of oils, wetters, adjuvants, or fertilizer 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.
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 agro-chemical 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, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
The mixtures of the invention are suitable for use in protecting crops, plants, plant propagation materials, e.g. seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, e.g. seeds, or soil or water, in which the plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of a mixture of the invention.
The mixtures of the invention are also suitable for use in combating or controlling animal pests. Therefore, the invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, e.g. seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a mixture of the invention.
The mixtures of the invention are effective through both contact and ingestion to any and all developmental stages, such as egg, larva, pupa, and adult.
The mixtures of the invention can be applied as such or in form of compositions comprising them.
The application can be carried out both before and after the infestation of the crops, plants, plant propagation materials by the pests.
The term "contacting" includes both direct contact (applying the compounds/compositions directly on the animal pest or plant) and indirect contact (applying the compounds/compositions to the locus).
The term “animal pest” includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects.
The term “plant” includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g. sugar beet, or fodder beet; fruits, e.g. pomes, stone fruits, or soft fruits, e.g. apples, pears, plums, peaches, nectarines, almonds, cherries, papayas, strawberries, raspberries, blackberries or gooseberries; leguminous plants, e.g. beans, lentils, peas, alfalfa, or soybeans; oil plants, e.g. rapeseed (oilseed rape), turnip rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts, or soybeans; cucurbits, e.g. squashes, pumpkins, cucumber or melons; fiber plants, e.g. cotton, flax, hemp, or jute; citrus fruit, e.g. oranges, lemons, grape-fruits or mandarins; vegetables, e.g. eggplant, spinach, lettuce (e.g. iceberg lettuce), chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, e.g. avocados, cinnamon, or camphor; energy and raw material plants, e.g. corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines; hop; sweet leaf (Stevia); natural rubber plants or ornamental and forestry plants, shrubs, broad-leaved trees or evergreens, eucalyptus; turf; lawn; grass. Preferred plants include potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee, or sugar cane; fruits; vines; ornamentals; or vegetables, e.g. cucumbers, tomatoes, beans or squashes.
The term "cultivated plants" is to be understood as including plants which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.
Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome. Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect.
Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant in order to add a trait or improve a trait. These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, which differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include in particular herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
Herbicide tolerance has been created by using mutagenesis as well as using genetic engineering. Plants which have been rendered tolerant to ALS inhibitor herbicides by conventional methods of mutagenesis and breeding comprise plant varieties commercially available under the name Clearfield (trademark registered) .
Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides and HPPD inhibitors, like isoxaflutole and mesotrione.
Transgenes which have been used to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 and aad-12, for tolerance to dicamba: dmo, for tolerance to oxynil herbicies: bxn, for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA, for tolerance to ALS inhibitor herbicides: csr1-2, for tolerance to HPPD inhibitor herbicides: hppdPF, W336 and avhppd-03.
Transgenic corn events comprising herbicide tolerance genes are e.g., but not excluding others, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHG0JG, HCEM485, VCO-01981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.
Transgenic soybean events comprising herbicide tolerance genes are e.g., but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
Transgenic cotton events comprising herbicide tolerance genes are e.g., but not excluding others, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.
Transgenic canola events comprising herbicide tolerance genes are e.g., but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.
Insect resistance has mainly been created by transferring bacterial genes for insecticidal pro-teins to plants. Transgenes which have most frequently been used are toxin genes of Bacillus spec. and synthetic variants thereof, like cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A(a), vip3Aa20. However, also genes of plant origin have been transferred to other plants. In particular genes coding for protease inhibitors, like CpTI and pinII. A further approach uses transgenes in order to produce double stranded RNA in plants to target and downregulate in-sect genes. An example for such a transgene is dvsnf7.
Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA are e.g., but not excluding others, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098.
Transgenic soybean events comprising genes for insecticidal proteins are e.g., but not excluding others, MON87701, MON87751 and DAS-81419.
Transgenic cotton events comprising genes for insecticidal proteins are e.g., but not excluding others, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.
Increased yield has been created by increasing ear biomass using the transgene athb17, be-ing present in corn event MON87403, or by enhancing photosynthesis using the transgene bbx32, being present in the soybean event MON87712.
Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.
Tolerance to abiotic conditions, in particular to tolerance to drought, has been created by using the transgene cspB, comprised by the corn event MON87460 and by using the transgene Hahb-4, comprised by soybean event IND-00410-5.
Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process. Preferred combination of traits are herbicide tolerance to different groups of herbicides, insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, herbicide tolerance with one or several types of insect resistance, herbicide tolerance with increased yield as well as a combination of herbicide tolerance and tolerance to abiotic conditions.
Plants comprising singular or stacked traits as well as the genes and events providing these traits are known (http://www.isaaa.org/gmapprovaldatabase) and (http://cera-gmc.org/GMCropDatabase).
Further information on specific events and methods to detect them can be found for canola events MS1, MS8, RF3, GT73, MON88302, KK179 in WO01/031042, WO01/041558, WO01/041558, WO02/036831, WO11/153186, WO13/003558, for cotton events MON1445, MON15985, MON531(MON15985), LLCotton25, MON88913, COT102, 281-24-236, 3006-210-23, COT67B, GHB614, T304-40, GHB119, MON88701, 81910 in WO02/034946, WO02/100163, WO02/100163, WO03/013224, WO04/072235, WO04/039986, WO05/103266, WO05/103266, WO06/128573, WO07/017186, WO08/122406, WO08/151780, WO12/134808, WO13/112527, for corn events GA21, MON810, DLL25, TC1507, MON863, MIR604, LY038, MON88017, 3272, 59122, NK603, MIR162, MON89034, 98140, 32138, MON87460, 5307, 4114, MON87427, DAS40278, MON87411, 33121, MON87403, MON87419 in WO98/044140, US02/102582, US03/126634, WO04/099447, WO04/011601, WO05/103301, WO05/061720, WO05/059103, WO06/098952, WO06/039376, US2007/292854, WO07/142840, WO07/140256, WO08/112019, WO09/103049, WO09/111263, WO10/077816, WO11/084621, WO11/062904, WO11/022469, WO13/169923, WO14/116854, WO15/053998, WO15/142571, for potato events E12, F10, J3, J55, V11, X17, Y9 in WO14/178910, WO14/178913, WO14/178941, WO14/179276, WO16/183445, WO17/062831, WO17/062825, for rice events LLRICE06, LLRICE601, LLRICE62 in WO00/026345, WO00/026356, WO00/026345 for soybean events H7-1, MON89788, A2704-12, A5547-127, DP305423, DP356043, MON87701, MON87769, CV127, MON87705, DAS68416-4, MON87708, MON87712, SYHT0H2, DAS81419, DAS81419 x DAS44406-6, MON87751 in WO04/074492, WO06/130436, WO06/108674, WO06/108675, WO08/054747, WO08/002872, WO09/064652, WO09/102873, WO10/080829, WO10/037016, WO11/066384, WO11/034704, WO12/051199, WO12/082548, WO13/016527, WO13/016516, WO14/201235.
The use of compositions according to the invention on cultivated plants may result in effects which are specific to a cultivated plant comprising a certain gene or event. These effects may comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigor, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
It has been found that the pesticidal activity of the mixtures of the invention may be enhanced by the insecticidal trait of a modified plant. Furthermore, it has been found that the mixtures of the invention are suitable for preventing insects to become resistant to the insecticidal trait or for combating pests, which already have become resistant to the insecticidal trait of a modified plant. Moreover, the mixtures of the invention are suitable for combating pests, against which the insecticidal trait is not effective, so that a complementary insecticidal activity can advantageously be used.
The term "plant propagation material" refers to all the generative parts of the plant e.g. seeds and vegetative plant material e.g. 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. Seedlings and young plants, which are to be trans-planted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
The term “seed” embraces seeds and plant propagules including true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots, and means preferably true seeds.
"Pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions e.g. desired pesticidal effect and duration, weather, target species, locus, mode of application.
For use in treating crop plants, e.g. by foliar application, the rate of application of the active ingredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare.
The mixtures of the invention are also suitable for use against non-crop insect pests. For use against said non-crop pests, the mixture of the invention can be used as bait composition, gel, general insect spray, aero-sol, as ultra-low volume application and bed net (impregnated or surface applied).
The term “non-crop insect pest” refers to pests, which are particularly relevant for non-crop targets, e.g. ants, termites, wasps, flies, ticks, mosquitoes, bed bugs, crickets, or cockroaches, such as: Aedes aegypti, Musca domestica, Tribolium spp.; termites such as Reticulitermes flavipes, Coptotermes formosanus; roaches such as Blatella germanica, Periplaneta Americana; ants such as Solenopsis invicta, Linepithema humile, and Camponotus pennsylvanicus.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). For use in bait compositions, the typical content of active ingredient is from 0.001 wt% to 15 wt%, desirably from 0.001 wt% to 5 wt% of active compound.
The mixtures of the invention are suitable for efficiently combating animal pests e.g. arthropods, gastropods and nematodes including:
insects from the order of Lepidoptera, e.g. Achroia grisella, Acleris spp. e.g. A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. e.g. A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. e.g. A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A. subterranea; Alabama argillacea, Aleurodicus dispersus, Alsophila pometaria, Ampelophaga rubiginosa, Amyelois transitella, Anacampsis sarcitella, Anagasta kuehniella, Anarsia lineatella, Anisota senatoria, Antheraea pernyi, Anticarsia (=Thermesia) spp. e.g. A. gemmatalis; Apamea spp., Aproaerema modicella, Archips spp. e.g. A. argyrospila, A. fuscocupreanus, A. rosana, A. xyloseanus; Argyresthia conjugella, Argyroploce spp., Argyrotaenia spp. e.g. A. velutinana; Athetis mindara, Austroasca viridigrisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. e.g. C. murinana, C. podana; Cactoblastis cactorum, Cadra cautella, Calingo braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp. e.g. C. niponensis, C. sasakii; Cephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. e.g. C. Indicus, C. suppressalis, C. partellus; Choreutis pariana, Choristoneura spp. e.g. C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C. rosaceana; Chrysodeixis (=Pseudoplusia) spp., e.g. C. eriosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Cochylis hospes, Coleophora spp., Colias eurytheme, Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Corcyra cephalonica, Crambus caliginosellus, Crambus teterrellus, Crocidosema (=Epinotia) aporema, Cydalima (=Diaphania) perspectalis, Cydia (=Carpocapsa) spp., e.g. C. pomonella, C. latiferreana; Dalaca noctuides, Datana integerrima, Dasychira pinicola, Dendrolimus spp., e.g. D. pini, D. spectabilis, D. sibiricus; Desmia funeralis, Diaphania spp., e.g. D. nitidalis, D. hyalinata; Diatraea grandiosella, Diatraea saccharalis, Diphthera festiva, Earias spp. e.g. E. insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) curialis, Elasmopalpus lignosellus, Eldana saccharina, Endopiza viteana, Enno-mos subsignaria, Eoreuma loftini, Ephestia spp., e.g. E. cautella, E. elutella, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp. e.g. F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. e.g. G. funebrana, G. molesta, G. inopinata; Halysidota spp., Harrisina americana, Hedylepta spp., Helicoverpa spp. e.g. H. armigera (=Heliothis armigera), H. zea (=Heliothis zea); Heliothis spp. e.g. H. assulta, H. subflexa, H. virescens; Hellula spp. e.g. H. undalis, H. rogatalis; Helocoverpa gelotopoeon, Hemileuca oliviae, Herpetogramma licarsisalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homoeosoma electellum, Homona magnanima, Hypena scabra, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Kakivoria flavofasciata, Keiferia lycopersicella, Lambdina fiscellaria fiscellaria, Lambdina fiscellaria lugubrosa, Lamprosema indicata, Laspeyresia molesta, Leguminivora glycinivorella, Lerodea eufala, Leucinodes orbonalis, Leucoma salicis, Leucoptera spp. e.g. L. coffeella, L. scitella; Leuminivora lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo (=Amyna axis), Lobesia botrana, Lophocampa spp., Loxagrotis albicosta, Loxostege spp. e.g. L. sticticalis, L. cereralis; Lymantria spp., e.g. L. dispar, L. monacha; Lyonetia clerkella, Lyonetia prunifoliella, Malacosoma spp., e.g. M. americanum, M. californicum, M. constrictum, M. neu-stria; Mamestra spp., e.g. M. brassicae, M. configurata; Mamstra brassicae, Manduca spp. e.g. M. quinquemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mocis spp., e.g. M. lapites, M. repanda; Mocis latipes, Monochroa fragariae, Mythimna separata, Nemapogon cloacella, Neoleucinodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes indicata, Omphisa anastomosalis, Operophtera brumata, Orgyia pseudotsugata, Oria spp., Orthaga thyrisalis, Ostrinia spp. e.g. O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paranthrene regalis, Paysandisia archon, Pectinophora spp. e.g. P. gossypiella; Peridroma saucia, Perileucoptera spp., e.g. P. coffeella; Phalera bucephala, Phryganidia californica, Phthorimaea spp. e.g. P. operculella; Phyllocnistis citrella, Phyllonorycter spp. e.g. P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. e.g. P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathypena scabra, Platynota spp. e.g. P. flavedana, P. idaeusalis, P. stultana; Platyptilia carduidactyla, Plebejus argus, Plo-dia interpunctella, Plusia spp, Plutella maculipennis, Plutella xylostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus lepigone, Pseudaletia spp. e.g. P. sequax, P. unipuncta; Pyrausta nubilalis, Rachiplusia nu, Richia albicosta, Rhizobius ventralis, Rhyacionia frustrana, Sabulodes aegrotata, Schizura concinna, Schoenobius spp., Schreckensteinia festaliella, Scirpophaga spp. e.g. S. incertulas, S. innotata; Scotia segetum, Sesamia spp. e.g. S. inferens, Seudyra subflava, Sitotroga cerealella, Sparganothis pilleriana, Spilonota lechriaspis, S. ocelli-na, Spodoptera (=Lamphygma) spp. e.g. S. cosmoides, S. eridania, S. exigua, S. frugiperda, S. latisfascia, S. littoralis, S. litura, S. omithogalli; Stigmella spp., Stomopteryx subsecivella, Strymon bazochii, Sylepta derogata, Synanthedon spp. e.g. S. exitiosa, Tecia solanivora, Telehin licus, Thaumatopoea pityocampa, Thaumatotibia (=Cryptophlebia) leucotreta, Thaumetopoea pityocampa, Thecla spp., Theresimima ampelophaga, Thyrinteina spp, Tildenia inconspicuella, Tinea spp. e.g. T. cloacella, T. pellionella; Tineola bisselliella, Tortrix spp. e.g. T. viridana; Trichophaga tapetzella, Trichoplusia spp. e.g. T. ni; Tuta (=Scrobipalpula) absoluta, Udea spp. e.g. U. rubigalis, U. rubigalis; Virachola spp., Yponomeuta padella, and Zeiraphera canadensis;
insects from the order of Coleoptera, e.g. Acalymma vittatum, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus spp. e.g. A. anxius, A. planipennis, A. sinuatus; Agriotes spp. e.g. A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimallus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala corpulenta, Anomala rufocuprea, Anoplophora spp. e.g. A. glabripennis; Anthonomus spp. e.g. A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogonia spp., Athous haemorrhoidalis, Atomaria spp. e.g. A. linearis; Attagenus spp., Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. e.g. B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Callopistria floridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp. e.g. C. assimilis, C. napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp. e.g. C. vespertinus; Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryptorhynchus lapathi, Ctenicera spp. e.g. C. destructor; Curculio spp., Cylindrocopturus spp., Cyclocephala spp., Dac-tylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. e.g. D. undecimpunctata, D. speciosa, D. longicornis, D. semipunctata, D. virgifera; Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp. e.g. E. varivestis, E. vigintioctomaculata; Epitrix spp. e.g. E. hirtipennis, E. similaris; Eutheola humilis, Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera spp., e.g. H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp. e.g. L. bilineata, L. melanopus; Leptinotarsa spp. e.g. L. decemlineata; Leptispa pygmaea, Limonius californi-cus, Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp. e.g. L. bruneus; Liogenys fuscus, Macrodactylus spp. e.g. M. subspinosus; Maladera matrida, Megaplatypus mutates, Megascelis spp., Melanotus communis, Meligethes spp. e.g. M. aeneus; Melolontha spp. e.g. M. hippocastani, M. melolontha; Metamasius hemipterus, Microtheca spp., Migdolus spp. e.g. M. fryanus, Monochamus spp. e.g. M. alternatus; Naupactus xanthographus, Niptus hololeucus, Oberia brevis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema oryzae, Oxycetonia jucunda, Phaedon spp. e.g. P. brassicae, P. cochleariae; Phoracantha recurva, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp. e.g. P. helleri; Phyllotreta spp. e.g. P. chrysocephala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psacothea hilaris, Psylliodes chrysocephala, Prostephanus truncates, Psylliodes spp., Ptinus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp. e.g. R. billineatus, R. ferrugineus, R. palmarum, R. phoenicis, R. vulneratus; Saperda candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. e.g. S. granaria, S. oryzae, S. zeamais; Sphenophorus spp. e.g. S. levis; Stegobium paniceum, Sternechus spp. e.g. S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. e.g. T. castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp. e.g. X. pyrrhoderus; and, Zabrus spp. e.g. Z. tenebrioides;
insects from the order of Diptera e.g. Aedes spp. e.g. A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. e.g. A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bactrocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chrysomyia spp. e.g. C. bezziana, C. hominivorax, C. macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. e.g. C. hominivorax; Contarinia spp. e.g. C. sorghicola; Cordylobia anthropophaga, Culex spp. e.g. C. nigripalpus, C. pipiens, C. quinquefasciatus, C. tarsalis, C. tritaeniorhynchus; Culicoides furens, Culiseta inornata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasineura oxycoccana, Delia spp. e.g. D. antique, D. coarctata, D. platura, D. radicum; Dermatobia hominis, Drosophila spp. e.g. D. suzukii, Fannia spp. e.g. F. canicularis; Gastraphilus spp. e.g. G. intestinalis; Geomyza tipunctata, Glossina spp. e.g. G. fuscipes, G. morsitans, G. palpalis, G. tachinoides; Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. e.g. H. platura; Hypoderma spp. e.g. H. lineata; Hyppobosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp. e.g. L. sativae, L. trifolii; Lucilia spp. e.g. L. caprina, L. cuprina, L. sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. e.g. M. destructor; Musca spp. e.g. M. autumnalis, M. domestica; Muscina stabulans, Oestrus spp. e.g. O. ovis; Opomyza florum, Oscinella spp. e.g. O. frit; Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. e.g. P. antiqua, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis spp. e.g. R. cerasi, R. cingulate, R. indifferens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp. e.g. S. haemorrhoidalis; Simulium vittatum, Sitodiplosis mosellana, Stomoxys spp. e.g. S. calcitrans; Tabanus spp. e.g. T. atratus, T. bovinus, T. lineola, T. similis; Tannia spp., Thecodiplo-sis japonensis, Tipula oleracea, Tipula paludosa, and Wohlfahrtia spp;
insects from the order of Thysanoptera e.g., Baliothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. e.g. F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. e.g. S. citri, S. dorsalis, S. perseae; Stenchaetothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp. e.g. T. imagines, T. hawaiiensis, T. oryzae, T. palmi, T. parvispinus, T. tabaci;
insects from the order of Hemiptera e.g., Acizzia jamatonica, Acrosternum spp., e.g. A. hilare; Acyrthosipon spp., e.g. A. onobrychis, A. pisum; Adelges laricis, Adelges tsugae, Adelphocoris spp., e.g. A. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Aulacorthum solani, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. e.g. A. craccivora, A. fabae, A. forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pomi, A. sambuci, A. schneideri, A. spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacaspis yasumatsui, Aulacorthum solani, Bactericera cockerelli (Paratrioza cockerelli), Bemisia spp. e.g. B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp. e.g. B. leucopterus; Brachycaudus spp. e.g. B. cardui, B. helichrysi, B. persicae, B. prunicola; Brachycolus spp., Brachycorynella as-paragi, Brevicoryne brassicae, Cacopsylla spp. e.g. C. fulguralis, C. pyricola (Psylla piri); Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horni, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Cimex spp. e.g. C. hemipterus, C. lectularius; Coccomytilus halli, Coccus spp. e.g. C. hesperidum, C. pseudomagnoliarum; Corythucha arcuata, Creontiades dilutus, Cryptomyzus ribis, Chrysomphalus aonidum, Cryptomyzus ribis, Ctenarytaina spatulata, Cyrtopeltis notatus, Dalbulus spp., Dasynus piperis, Dialeurodes spp. e.g. D. citrifolii; Dalbulus maidis, Diaphorina spp. e.g. D. citri; Diaspis spp. e.g. D. bromeliae; Dichelops furcatus, Diconocoris hewetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. e.g. D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. e.g. D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empoasca spp. e.g. E. fabae, E. solana; Epidiaspis leperii, Eriosoma spp. e.g. E. lanigerum, E. pyricola; Erythroneura spp., Eurygaster spp. e.g. E. integriceps; Euscelis bilobatus, Euschistus spp. e.g. E. heros, E. impictiventris, E. servus; Fiorinia theae, Geococcus coffeae, Glycaspis brimblecombei, Halyomorpha spp. e.g. H. halys; Heliopeltis spp., Homalodisca vitripennis (=H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lactucae, Icerya spp. e.g. I. purchase; Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp. e.g. L. ulmi; Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp. e.g. L. hesperus, L. lineolaris, L. praten-sis; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macrosiphum spp. e.g. M. rosae, M. avenae, M. euphorbiae; Macrosteles quadrilineatus, Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Melanocallis (=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia costalis, Mo-nelliopsis pecanis, Myzocallis coryli, Murgantia spp., Myzus spp. e.g. M. ascalonicus, M. cerasi, M. nicotianae, M. persicae, M. varians; Nasonovia ribisnigri, Neotoxoptera formosana, Neomegalotomus spp, Nephotettix spp. e.g. N. malayanus, N. nigropictus, N. parvus, N. vires-cens; Nezara spp. e.g. N. viridula; Nilaparvata lugens, Nysius huttoni, Oebalus spp. e.g. O. pugnax; Oncometopia spp., Orthezia praelonga, Oxycaraenus hyalinipennis, Parabemisia myricae, Parlatoria spp., Parthenolecanium spp. e.g. P. corni, P. persicae; Pemphigus spp. e.g. P. bursarius, P. populivenae; Peregrinus maidis, Perkinsiella saccharicida, Phenacoccus spp. e.g. P. aceris, P. gossypii; Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp. e.g. P. devastatrix, Piesma quadrata, Piezodorus spp. e.g. P. guildinii; Pinnaspis aspidistrae, Planococcus spp. e.g. P. citri, P. ficus; Prosapia bicincta, Protopulvinaria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. e.g. P. comstocki; Psylla spp. e.g. P. mali; Pteromalus spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., e.g. Q. perniciosus; Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. e.g. R. pseudobrassicas, R. insertum, R. maidis, R. padi; Sagatodes spp., Sahlbergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mali, Scaptocoris spp., Scaphoides titanus, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insularis, Spissistilus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis maculate, Thyanta spp. e.g. T. accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp. e.g. T. aurantii; Trialeurodes spp. e.g. T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. e.g. U. citri, U. yanonensis; and Viteus vitifolii,
Insects from the order Hymenoptera e.g. Acanthomyops interjectus, Athalia rosae, Atta spp. e.g. A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A. sexdens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp. e.g. C. floridanus, C. pennsylvanicus, C. modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmex spp., Dryocosmus kuriphilus, Formica spp., Hoplocampa spp. e.g. H. minuta, H. testudinea; Iridomyrmex humilis, Lasius spp. e.g. L. niger, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp. e.g. M. pharaonis, Monomorium, Nylandria fulva, Pachycondyla chinensis, Paratrechina longicornis, Paravespula spp., e.g. P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. e.g. P. megacephala; Pogonomyrmex spp. e.g. P. barbatus, P. californicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cyaneus, Solenopsis spp. e.g. S. geminata, S.invicta, S. molesta, S. richteri, S. xyloni, Sphecius speciosus, Sphex spp., Tapinoma spp. e.g. T. melanocephalum, T. sessile; Tetramorium spp., e.g. T. caespitum, T. bicarinatum, Vespa spp., e.g. V. crabro; Vespula spp., e.g. V. squamosal; Wasmannia auropunctata, Xylocopa sp;
Insects from the order Orthoptera e.g. Acheta domesticus, Calliptamus italicus, Chortoicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp. e.g. G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. e.g. L. migratoria, L. pardalina; Melanoplus spp. e.g. M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris septemfasciata, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp. e.g. S. americana, S. gregaria, Stemopelmatus spp., Tachycines asynamorus, and Zonozerus variegatus;
Pests from the Class Arachnida e.g. Acari,e.g. of the families Argasidae, Ixodidae and Sar-coptidae, e.g. Amblyomma spp. (e.g. A. americanum, A. variegatum, A. maculatum), Argas spp. e.g. A. persicu), Boophilus spp. e.g. B. annulatus, B. decoloratus, B. microplus, Dermacentor spp. e.g. D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. e.g. H. truncatum, Ixodes spp. e.g. I. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp. e.g. O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. e.g. P. ovis, Rhipicephalus spp. e.g. R. sanguineus, R. appendiculatus, Rhipicephalus evertsi, Rhizoglyphus spp., Sarcoptes spp. e.g. S. Scabiei; and Family Eriophyidae including Aceria spp. e.g. A. sheldoni, A. anthocoptes, Acallitus spp., Aculops spp. e.g. A. lycopersici, A. pelekassi; Aculus spp. e.g. A. schlechtendali; Colomerus vitis, Epitrimerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp. e.g. Eriophyes sheldoni; Family Tarsonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Stenotarsonemus spp. Steneotarsonemus spinki; Family Tenuipalpidae including Brevipalpus spp. e.g. B. phoenicis; Family Tetranychidae including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp. e.g. T. cinnabarinus, T. evansi, T. kanzawai, T, pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praetiosa; Panonychus spp. e.g. P. ulmi, P. citri; Metatetranychus spp. and Oligonychus spp. e.g. O. pratensis, O. perseae, Vasates lycopersici; Raoiella indica, Family Carpoglyphidae including Carpoglyphus spp.; Penthaleidae spp. e.g. Halotydeus destructor; Family Demodicidae with species e.g. Demodex spp.; Family Trombicidea including Trombicula spp.; Family Macronyssidae including Ornothonyssus spp.; Family Pyemotidae including Pyemotes tritici; Tyrophagus putrescentiae; Family Acaridae includ-ing Acarus siro; Family Araneida including Latrodectus mactans, Tegenaria agrestis, Chi-racanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles reclusa;
Pests from the Phylum Nematoda, e.g. plant parasitic nematodes e.g. root-knot nematodes, Meloidogyne spp. e.g. M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. e.g. G. rostochiensis; Heterodera spp. e.g. H. avenae, H. glycines, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelenchoides spp. e.g. A. besseyi; Sting nematodes, Belonolaimus spp. e.g. B. longicaudatus; Pine nematodes, Bursaphelenchus spp. e.g. B. lignicolus, B. xylophilus; Ring nematodes, Criconema spp., Criconemella spp. e.g. C. xenoplax and C. ornata; and, Criconemoides spp. e.g. Criconemoides informis; Mesocriconema spp.; Stem and bulb nematodes, Ditylenchus spp. e.g. D. destructor, D. dipsaci; Awl nematodes, Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; Sheath and sheathoid nematodes, Hemicycliophora spp. and Hemicriconemoides spp.; Hirshmanniella spp.; Lance nematodes, Hoploaimus spp.; False rootknot nematodes, Nacobbus spp.; Needle nematodes, Longidorus spp. e.g. L. elongatus; Lesion nematodes, Pratylenchus spp. e.g. P. brachyurus, P. neglectus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nema-todes, Radopholus spp. e.g. R. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp. e.g. R. robustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. e.g. T. obtusus, T. primitivus; Paratrichodorus spp. e.g. P. minor; Stunt nematodes, Tylenchorhynchus spp. e.g. T. claytoni, T. dubius; Citrus nematodes, Tylenchulus spp. e.g. T. semipenetrans; Dagger nematodes, Xiphinema spp.; and other plant parasitic nematode species;
Insects from the order Blattodea e.g. Macrotermes spp. e.g. M. natalensis; Cornitermes cu-mulans, Procornitermes spp., Globitermes sulfureus, Neocapritermes spp. e.g. N. opacus, N. parvus; Odontotermes spp., Nasutitermes spp. e.g. N. corniger; Coptotermes spp. e.g. C. for-mosanus, C. gestroi, C. acinaciformis; Reticulitermes spp. e.g. R. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. virginicus; Heterotermes spp. e.g. H. aureus, H. longiceps, H. tenuis; Cryptotermes spp. e.g. C. brevis, C. cavifrons; Incisitermes spp. e.g. I. minor, I. snyderi; Marginitermes hubbardi, Kalotermes flavicollis, Neotermes spp. e.g. N. cas-taneus, Zootermopsis spp. e.g. Z. angusticollis, Z. nevadensis, Mastotermes spp. e.g. M. dar-winiensis; Blatta spp. e.g. B. orientalis, B. lateralis; Blattella spp. e.g. B. asahinae, B. germanica; Rhyparobia maderae, Panchlora nivea, Periplaneta spp. e.g. P. americana, P. australasiae, P. brunnea, P. fuliginosa, P. japonica; Supella longipalpa, Parcoblatta pennsylvanica, Eurycotis floridana, Pycnoscelus surinamensis,
Insects from the order Siphonoptera e.g. Cediopsylla simples, Ceratophyllus spp., Ctenoce-phalides spp. e.g. C. felis, C. canis, Xenopsylla cheopis, Pulex irritans, Trichodectes canis, Tunga penetrans, and Nosopsyllus fasciatus,
Insects from the order Thysanura e.g. Lepisma saccharina, Ctenolepisma urbana, and Thermobia domestica,
Pests from the class Chilopoda e.g. Geophilus spp., Scutigera spp. e.g. Scutigera coleoptrata;
Pests from the class Diplopoda e.g. Blaniulus guttulatus, Julus spp., Narceus spp.,
Pests from the class Symphyla e.g. Scutigerella immaculata,
Insects from the order Dermaptera, e.g. Forficula auricularia,
Insects from the order Collembola, e.g. Onychiurus spp., e.g. Onychiurus armatus,
Pests from the order Isopoda, e.g. Armadillidium vulgare, Oniscus asellus, Porcellio scaber,
Insects from the order Phthiraptera, e.g. Damalinia spp., Pediculus spp. e.g. Pediculus hu-manus capitis, Pediculus humanus corporis, Pediculus humanus humanus; Pthirus pubis, Haematopinus spp. e.g. Haematopinus eurysternus, Haematopinus suis; Linognathus spp. e.g. Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp.,
Further pest species which may be controlled by compounds I and its mixtures include: from the Phylum Mollusca, class Bivalvia, e.g., Dreissena spp.; class Gastropoda, e.g., Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, Succinea spp.; from the class of the helminths, e.g., Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp. e.g. Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuel-leborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.
The mixtures of the invention are also suitable as fungicides effective against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, in particular from the classes of Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (syn. Fungi imperfecti). They can be used in crop protection as foliar fungicides, fungicides for seed dressing, and soil fungicides.
The compounds I and the mixture and compositions thereof are preferably useful in the control of phytopathogenic fungi on various plants, as described herein.
The mixtures of the invention are particularly suitable for controlling the following causal agents of 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 (e.g. A. dauci or A. porri), oilseed rape (A. brassicicola or brassicae), sugar beets (A. tenuis), fruits (e.g. A. grandis), rice, soybeans, potatoes and tomatoes (e.g. A. solani, A. grandis or A. alternata), tomatoes (e.g. A. solani or A. alternata) and wheat (e.g. A. triticina); 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; Aureobasidium zeae (syn. Kapatiella zeae) on corn; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e.g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e.g. spot blotch (B. sorokiniana) on cereals and e.g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e.g. strawberries), vegetables (e.g. lettuce, carrots, celery and cabbages); B. squamosa or B. allii on onion family), oilseed rape, ornamentals (e.g. B eliptica), 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; Cladobotryum (syn. Dactylium) spp. (e.g. C. mycophilum
(formerly Dactylium dendroides, teleomorph: Nectria albertinii, Nectria rosella syn. Hypomyces rosellus) on mushrooms; 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), soybeans (e.g. C. truncatum or C. gloeosporioides), vegetables (e.g. C. lagenarium or C. capsici), fruits (e.g. C. acutatum), coffee (e.g. C. coffeanum or C. kahawae) and C. gloeosporioides on various crops; Corticium spp., e.g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans, cotton 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 (formerly 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, oilseed 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 (f. sp. glycines now syn. F. virguliforme ) and F. tucumaniae and F. brasiliense each causing sudden death syndrome 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 bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e.g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals, potatoes 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 (syn. Monilia spp.: 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: Zymoseptoria tritici formerly Septoria tritici: Septoria blotch) on wheat or M. fijiensis (syn. Pseudocercospora fijiensis: black Sigatoka disease) and M. musicola on bananas, M. arachidicola (syn. M. arachidis or Cercospora arachidis), M. berkeleyi on peanuts, M. pisi on peas and M. brassiciola on brassicas; Peronospora spp. (downy mildew) on cabbage (e.g. P. brassicae), oilseed 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 (syn. Leptosphaeria biglobosa and L. maculans: root and stem rot) on oilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off) on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn; 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,oilseed 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) and curcurbits (P. xanthii); 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 (syn. Oculimacula yallundae, O. acuformis: 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; Pyrenopeziza spp., e.g. P. brassicae on oilseed rape; 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, oilseed rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e.g. P. ultimum or P. aphanidermatum) and P. oligandrum on mushrooms; Ramularia spp., e.g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley, R. areola (teleomorph: Mycosphaerella areola) on cotton and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, oilseed 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 and R. commune (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables (S. minor and S. sclerotiorum) and field crops, such as oilseed rape, sunflowers (e.g. S. sclerotiorum) and soybeans, S. rolfsii (syn. Athelia rolfsii) on soybeans, peanut, vegetables, corn, cereals and ornamentals; Septoria spp. on various plants, e.g. S. glycines (brown spot) on soybeans, S. tritici (syn. Zymoseptoria 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; Setosphaeria spp. (leaf blight) on corn (e.g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e.g. S. reiliana, syn. Ustilago reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (syn. Podosphaera xanthii: 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, syn. Septoria 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; Trichoderma harzianum on mushrooms; 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), sugar beets (e.g. U. betae or U. beticola) and on pulses (e.g. U. vignae, U. pisi, U. viciae-fabae and U. fabae); 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. longisporum on oilseed rape, V. dahliae on strawberries, oilseed rape, potatoes and tomatoes, and V. fungicola on mushrooms; Zymoseptoria tritici on cereals.
The compounds I and mixtures and compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases: rusts on soybean and cereals (e.g. Phakopsora pachyrhizi and P. meibomiae on soy; Puccinia tritici and P. striiformis on wheat); molds on specialty crops, soybean, oil seed rape and sunflowers (e.g. Botrytis cinerea on strawberries and vines, Sclerotinia sclerotiorum, S. minor and S. rolfsii on oil seed rape, sunflowers and soybean); Fusarium diseases on cereals (e.g. Fusarium culmorum and F. graminearum on wheat); downy mildews on specialty crops (e.g. Plasmopara viticola on vines, Phytophthora infestans on potatoes); powdery mildews on specialty crops and cereals (e.g. Uncinula necator on vines, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals); and leaf spots on cereals, soybean and corn (e.g. Septoria tritici and S. nodorum on cereals, S. glycines on soybean, Cercospora spp. on corn and soybean).
The mixtures of the invention are particularly useful in seed treatment and soil treatment.
The term “seed treatment” comprises e.g. seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods. Preferably, the seed treatment application of the active compounds or mixtures thereof is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
The invention also comprises seeds coated with or containing the active compounds or mixtures thereof. The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.
Suitable seed is e.g. seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, e.g. seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants e.g. potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
In addition, the active compound or mixtures may also be used for the treatment of seeds from plants, which have been modified by mutagenisis or genetic engineering, and which e.g. tolerate the action of herbicides or fungicides or insecticides, as explained above for cultivated plants.
Conventional seed treatment formulations include e.g. flowable concentrates FS, solutions LS, suspoemulsions (SE), powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. Preferably, the formulations are applied such that germination is not included.
The active substance concentrations in ready-to-use formulations, which may be obtained after two-to-tenfold dilution, are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40% by weight.
In a preferred embodiment a FS formulation is used for seed treatment. Typically, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l anti-freezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Especially preferred FS formulations of the compounds and mixtures of the invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20% by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5% by weight of a wetter and from 0.5 to 15% by weight of a dispersing agent, up to 20% by weight, e.g. from 5 to 20% of an anti-freeze agent, from 0 to 15% by weight, e.g. 1 to 15% by weight of a pigment and/or a dye, from 0 to 40% by weight, e.g. 1 to 40% by weight of a binder (sticker/adhesion agent), optionally up to 5% by weight, e.g. from 0.1 to 5% by weight of a thickener, optionally from 0.1 to 2% of an anti-foam agent, and optionally a preservative e.g. a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1% by weight and a filler/vehicle up to 100% by weight.
In the treatment of seed, the application rates of the compounds and mixtures of the invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.
The invention therefore also relates to seed comprising a compound of the invention, or an agriculturally useful salt thereof, as defined herein. The amount of the compound of the invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops e.g. lettuce the rate can be higher.
Biological Examples of the Invention
The invention is now illustrated in further details by the following examples.
Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds (zero-interaction). The presence of a synergistic effect in terms of percent control, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 20-22):
When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.
The analysis of synergism or antagonism between the mixtures or compositions can be determined using Colby’s equation.
To quantify the degree of drug synergy, several furthermodels have been proposed, such as those based on the Highest single agent model (HAS, or Gaddum additivity) (Berenbaum, 1989), the Loewe additivity model (Loewe, 1953) and the Bliss independence model (Bliss, 1939).
In the present case, the two mixing partners are acting mutually non-exclusively active, i.e. the Bliss independence model seems to be most appropriate to describe the zero-interaction effect (Greco et al., 1992), where yBLISS is the expected effect based on the single effects of compound y1 and y2, respectively (1).
An R-script called “syngergyfinder” based on the model above was published by
He, L. et al. (2018).
The latest up-date was published by:
Zheng S, Wang W, Aldahdooh J, Malyutina A, Shadbahr T, Tanoli Z, Pessia A, Tang J (2022). “SynergyFinder Plus: Toward Better Interpretation and Annotation of Drug Combination Screening Datasets.” Genomics, Proteomics & Bioinformatics, 20(3):587-596. https://doi.org/10.1016/j.gpb.2022.01.004.
It can be also downloaded from Bioconductor.org:
https://bioconductor.org/packages/release/bioc/html/synergyfinder.html
When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.
The following tests demonstrate the control efficacy of compounds, mixtures or compositions of this invention on specific pests. However, the pest control protection afforded by the compounds, mixtures or compositions is not limited to these species. In certain instances, combinations of a compound of this invention with other invertebrate pest control compounds or agents are found to exhibit synergistic effects against certain important invertebrate pests.
If not otherwise specified, the test solutions are prepared as follow:
The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water : acteone. The test solution is prepared at the day of use.
Test solutions are prepared in general at concentrations of 1000 ppm, 500 ppm, 300 ppm, 100 ppm and 30 ppm (wt/vol).
1. Dalbulus maidis (corn leafhopper)
For evaluating control of Dalbulus maidis through contact or systemic means from seed treatment application, the test consisted of treated corn seeds planted in greenhouse containers in a randomized complete block design with four replications. The single compounds or mixture were applied to the seeds, and the seeds were planted into the boxes. Adult and immature D. maidis were transferred into the boxes after the seeds germinated. D. maidis efficacy was visually assessed per treatment. The mixture had a surprisingly higher effect than expected, i.e., higher than the expected combined control effect of the mixture partners.
2. Diceraeus melacanthus (green-belly stink bug)
For evaluating control of Diceraeus melacanthus through contact or systemic means from seed treatment application, the test consisted of treated corn seeds planted in greenhouse containers in a randomized complete block design with four replications. The single compounds or mixture were applied to the seeds, and the seeds were planted into the boxes. Adult D. melacanthus were transferred into the boxes after the seeds germinated. Plant damage from D. melacanthus was visually assessed per treatment. The mixture had a surprisingly higher effect than expected, i.e., higher than the expected combined control effect of the mixture partners.
3. Elasmopalpus lignosellus (lesser cornstalk borer)
For evaluating control of Elasmopalpus lignosellus through contact or systemic means from seed treatment application, the test consisted of treated soybean seeds planted in greenhouse containers in a randomized complete block design with four replications. The single compounds or mixture were applied to the seeds, and the seeds were planted into the boxes. Late-instar E. lignosellus were transferred into the boxes after the seeds germinated. Plant damage from E. lignosellus was visually assessed per treatment. The mixture had a surprisingly higher effect than expected, i.e., higher than the expected combined control effect of the mixture partners.
4. Helicoverpa armigera (cotton bollworm or corn earworm)
For evaluating control of Helicoverpa armigera through contact or systemic means from seed treatment application, the test consisted of treated soybean seeds planted in greenhouse containers in a randomized complete block design with four replications. The single compounds or mixture were applied to the seeds, and the seeds were planted into the boxes. Late-instar H. armigera were transferred into the boxes after the seeds germinated. Plant damage from H. armigera was visually assessed per treatment. The mixture had a surprisingly higher effect than expected, i.e., higher than the expected combined control effect of the mixture partners.
5. Melanotus spp. (typical click beetles), Phyllophaga spp. (May beetles, or June bugs), and other early-season soil pests of corn
For evaluating control of Melanotus spp., Phyllophaga spp., and other early-season soil pests through contact or systemic means from seed treatment application, the test consisted of treated corn seeds planted in a field in a randomized complete block design with four replications. The single compounds or mixture were applied to the seeds, and the seeds were planted into the field. A naturally-occurring population of early-season soil pests was utilized for the test. Plant stand reduction was visually assessed per treatment. The mixture had a surprisingly higher effect than expected, i.e., higher than the expected combined control effect of the mixture partners.
6. Melanotus spp. (typical click beetles), Phyllophaga spp. (May beetles, or June bugs), and other early-season soil pests of corn
For evaluating control of Melanotus spp., Phyllophaga spp., and other early-season soil pests through contact or systemic means from seed treatment application, the test consisted of treated corn seeds planted in a field in a randomized complete block design with four replications. The single compounds or mixture were applied to the seeds, and the seeds were planted into the field. A naturally-occurring population of early-season soil pests was utilized for the test. Plant stand reduction was visually assessed per treatment. The mixture had a surprisingly higher effect than expected, i.e., higher than the expected combined control effect of the mixture partners.
7. Limonius spp. (genus of click beetles), Agriotes spp. (genus of lined click beetle), and other early-season soil pests of cereals
For evaluating control of Limonius spp., Agriotes spp., and other early-season soil pests of cereals through contact or systemic means from seed treatment application, the test consisted of treated wheat seeds planted in a field in a randomized complete block design with four replications. The single compounds or mixture were applied to the seeds, and the seeds were planted into the field. A naturally-occurring population of early-season soil pests was utilized for the test. Plant stand reduction was visually assessed per treatment. The mixture had a surprisingly higher effect than expected, i.e., higher than the expected combined control effect of the mixture partners.
8. Phyllotreta striolata (yellow striped flea beetle) and Phyllotreta Cruciferae (crucifer flea beetle)
For evaluating control of Phyllotreta striolata and Phyllotreta Cruciferae through contact or systemic means from seed treatment application, the test consisted of treated canola seeds planted in a field in a randomized complete block design with four replications. The single compounds or mixture were applied to the seeds, and the seeds were planted into the field. A naturally-occurring population of P. striolata and P. Cruciferae was utilized for the test. Plant damage from P. striolata and P. Cruciferae was visually assessed per treatment. The mixture had a surprisingly higher effect than expected, i.e., higher than the expected combined control effect of the mixture partners.
Further, the following tests can be used to determine the fungicidal activity of the mixtures and a potential synergistic activity:
Fungicidal microtests
The active compounds are formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
The stock solutions are mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
The test is performed as described for each pathogen below.
The plates are placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs are measured at 405 nm 7 days after the inoculation.
The measured parameters are compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.
These percentages are converted into efficacies.
An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens are not growing.
The expected efficacies of active compound mixtures are determined using Colby's formula [R.S. Colby, “Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacies.
Test F1. Activity against the grey mold Botrytis cinerea in the microtiterplate test (BOTRCI)
A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution is then added.
Test F2. Activity against rice blast Pyricularia oryzae in the microtiterplate test (PYRIOR)
A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution is then added.
Test F3. Activity against leaf blotch on wheat caused by Septoria tritici (SEPTTR)
A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution is then added.
Test F4. Activity against anthracnose caused by Colletotrichum orbiculare in the microtiterplate test (COLLLA)
A spore suspension of Colletotrichum orbiculare in an aqueous bio malt solution is then added.
Simplified activity evaluation test of each mixture by Leaf Disc
The following tests were conducted, with different mixing ratios for the above effective seed treatments, to determine that similar synergistic effects should be achieved as expected.
9. Aulacophora spp. / Aulacophora femoralis (cucurbit leaf beetle)
Test Method: In the single agents or mixtures at various concentrations were immersed a 7 cm diameter cucumber leaf disc for 30 seconds, the immersed leaf discs were air dried and placed in a plastic petri dish, three adult Aulacophora femoralis were inoculated in each petri dish and then covered with a lid.
4 days after inoculation, the area percentage of the cucumber leaf discs eaten was surveyed, and the percentage of feeding damage suppression was calculated using the following formula (1).
formula(1): Feeding suppression rate(%)
= (feeding rate in untreated plot - feeding rate in treated plot)× 100 / feeding rate in untreated plot
10. Spodoptera spp. / Spodoptera litura (common cutworm)
Test Method:
In the single agents or mixtures at various concentrations was immersed a 7 cm diameter cabbage leaf disc for 30 seconds, the immersed leaf discs were air dried and placed in a plastic petri dish, five Spodoptera litura of 3rd instar were inoculated in each petri dish and then covered with a lid.
4 days after inoculation, the area percentage of the cabbage leaf discs eaten was surveyed, and the percentage of feeding damage suppression was calculated using the above formula (1).
11. Aphis spp. / Aphis gossypii (cotton aphid)
Test Method:
In the single agents or mixtures at various concentrations was immersed a 7 cm diameter cucumber leaf disc for 30 seconds, the immersed leaf discs were air dried and fixed with agar, 8 adult Aphis gossypii Glover were inoculated in each petri dish and then covered with a lid.
5 days after inoculation, the number of infesting Aphis gossypii on the cucumber leaf disc was counted, and the control value was calculated using the following formula (2).
formula (2): Control value={(T-C)/T}×100
T: number of infestants after treating in the untreated group,
C: number of infestants after treating in the treated group.
As described above, it was confirmed that the same synergistic effect is achieved even if the mixing ratio is changed in the above mixing.

Claims (21)

  1. Pesticidal mixtures comprising as active components
    A) the compound I which is selected from the compound I-1 of formula I-1:
    and
    B) at least one further compound II selected from the groups of:
    Group F (fungicides): F.1:-Azoxystrobin, F.2:-Trifloxystrobin, F.3:-Picoxystrobin, F.4:-Pyraclostrobin, F.5:-Mandestrobin, F.66: fluoxastrobin, F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.9:-Bixafen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.15:-Fluindapyr, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-Isoflucypram, F.19:-Cyclobutrifluram, F.20:-Oxathiapiprolin, F.21:-Fluoxapiprolin, F.22:-Metalaxyl, F.23:-Metalaxyl-M, F.24:-Picarbutrazox, F.25:-Ethaboxam, F.26:-Dimethomorph, F.27:-Fluopicolide, F.28:-Cyproconazole, F.29:-Difenoconazole, F.30:-Prothioconazole, F.31:-Flutriafol, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.41:-Fluoxytioconazole, F.42:-Fludioxinil, F.43:-Thiabendazole, F.44:-Silthiofam, F.45:-Fluazinam, F.46:-Ziram, F.47:-Thiram, F.48:-Carbendazim, F.49:-Thiophanate-methyl, F.50:-Valifenalate, F.51:-Diclobenthiazox, F.52:-Tolclofos-methyl, F.53:-Hymexazol, F.54:-Flumetylsulforim, F.55:-Fenpicoxamide, F.56:-Florylpicoxamid, F.57:-Metarylpicoxamid, F.58:-Natamycin, F.59:-Mandipropamid, F.60:-Flutolanil, F.61:-Fenamidone, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil;
    Group In (insecticides): In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.4: Dinotefuran, In.5: Thiacloprid, In.6: Acetamiprid, In.7: Sulfoxaflor, In.8: Flupyradifurone, In.9: Triflumezopyrim, In.10: Dicloromezotiaz , In.11: Fenmezoditiaz, In.12: Flupyrimin, In.13: Tefluthrin, In.14: Bifenthrin, In.15: Cypermethrin, In.16: alpha-Cypermethrin, In.17: zeta-Cypermethrin, In.18: lambda-Cyhalothrin, In.19: beta-Cyfluthrin, In.20: Thiodicarb, In.21: Methiocarb, In.22: Acephate, In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.25: Tetraniliprole, In.26: Cyclaniliprole, In.27: Fipronil, In.28: Isocycloseram, In.29: Fluxametamide, In.30: Broflanilide, In.31: Nicofluprole, In.32: Tigolaner, In.33: Dimpropyridaz, In.34: Spinosad, In.35: Spinetoram, In.36: Spirotetramat, In.37: Spiropidion, In.38: Spidoxamat, In.39: Abamectin, In.40: Afidopyropen, In.41: Tyclopyrazoflor, In.42: Tiapyrachlor, In.43: Indazapyroxamet, In.44: Indacyclometamide, In.45: Benzpyrimoxan, In.46: Flometoquin, In.47: Cyetpyrafen, In.48: Pyflubumide, In.49: Oxazosulfyl;
    Group N (nematicides): N.1: Tioxazafen, N.2: Fluazaindolizine, N.3: Flufensulfone, N.4: Flupentiofenox, N.5: Sulfiflumin, Biopesticides: N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), N.9: B. thuringiensis EX297512, N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.16: Bacillus amyloliquefaciens velezensis MBI600;
    wherein compound I and compound II are present in a weight ratio of from 1000:1 to 1:1000.
  2. The mixtures of claim 1 wherein component B) is selected from fungicides F.1:-Azoxystrobin, F.2:-Trifloxystrobin, F.3:-Picoxystrobin, F.4:-Pyraclostrobin, F.5:-Mandestrobin, F.66: fluoxastrobin, F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-Isoflucypram, F.19:-Cyclobutrifluram, F.20:-Oxathiapiprolin, F.21:-Fluoxapiprolin, F.22:-Metalaxyl, F.23:-Metalaxyl-M, F.24:-Picarbutrazox, F.25:-Ethaboxam, F.29:-Difenoconazole, F.30:-Prothioconazole, F.31:-Flutriafol, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.41:-Fluoxytioconazole, F.42:-Fludioxinil, F.43:-Thiabendazole, F.45:-Fluazinam, F.47:-Thiram, F.49:-Thiophanate-methyl, F.58:-Natamycin, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil.
  3. The mixtures of claim 2 wherein component B) is selected from the strobilurins F.1:-Azoxystrobin, F.2:-Trifloxystrobin, F.3:-Picoxystrobin, F.4:-Pyraclostrobin, F.5:-Mandestrobin, F.66: fluoxastrobin.
  4. The mixtures of claim 2 wherein component B) is selected from the SDHI inhibitors F.6:-Sedaxane, F.7:-Penthiopyrad, F.8:-Penflufen, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.12:-Boscalid, F.13:-Carboxin, F.14:-Pydiflumetofen, F.16:-Inpyrfluxam, F.17:-Pyrapropoyne, F.18:-Isoflucypram, F.19:-Cyclobutrifluram.
  5. The mixtures of claim 2 wherein component B) is selected from oomycetes fungicides F.20:-Oxathiapiprolin, F.21:-Fluoxapiprolin, F.22:-Metalaxyl, F.23:-Metalaxyl-M, F.24:-Picarbutrazox, F.25:-Ethaboxam.
  6. The mixtures of claim 2 wherein component B) is selected from the DMI fungicides (azoles) F.29:-Difenoconazole, F.30:-Prothioconazole, F.31:-Flutriafol, F.32:-Myclobutanil, F.33:-Ipconazole, F.34:-Tebuconazole, F.35:-Mefentrifluconazole, F.36:-Triadimenol, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.41:-Fluoxytioconazole.
  7. The mixtures of claim 1 wherein component B) is selected from insecticides In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.4: Dinotefuran, In.6: Acetamiprid, In.8: Flupyradifurone, In.12: Flupyrimin, In.13: Tefluthrin, In.14: Bifenthrin, In.19: beta-Cyfluthrin, In.20: Thiodicarb, In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.25: Tetraniliprole, In.26: Cyclaniliprole, In.27: Fipronil, In.28: Isocycloseram, In.30: Broflanilide, In.31: Nicofluprole, In.32: Tigolaner, In.33: Dimpropyridaz, In.39: Abamectin, In.49: Oxazosulfyl.
  8. The mixtures of claim 7, wherein component B) is selected from In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.4: Dinotefuran, In.6: Acetamiprid, In.8: Flupyradifurone, In.12: Flupyrimin, in particular In.1: Clothianidin, In.2: Thiamethoxam, In.3: Imidacloprid, In.6: Acetamiprid.
  9. The mixtures of claim 7, wherein component B) is selected from the diamides In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.25: Tetraniliprole, In.26: Cyclaniliprole.
  10. The mixtures of claim 1 wherein component B) is selected from nematicides In.20: Thiodicarb, In.39: Abamectin, F.10: Fluopyram, F.19: Cyclobutrifluram, N.1: Tioxazafen, N.2: Fluazaindolizine, N.3: Flufensulfone, N.4: Flupentiofenox, N.5: Sulfiflumin.
  11. The mixtures of claim 1 wherein component B) is selected from the biopesticide nematicides: N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), N.9: B. thuringiensis EX297512, N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.16: Bacillus amyloliquefaciens velezensis MBI600.
  12. The mixtures of claim 1 wherein component B) is selected from the biopesticide nematicides: N.6: Pasteuria nishizawae (Clariva), N.7: Burkholderia rinojensis A 396, N.8: Bacillus firmus I1582 (VOTIVO), F.10 Fluopyram + N.8, N.9: B. thuringiensis EX297512, N.8: + N.9 (VOTIVO 2.0), N.10: Bacillus amyloliquefaciens PTA-4838 (Aveo EZ/Varnimo), N.11: Bacillus licheniformis FMCH001, N.12: Bacillus subtilis FMCH002, N.11: + N.12 (Presence/Avodigen), N.13: Chromobacterium subtsugae PRAA4-T1, N.14: B. amyloliquefaciens F727, N.15: Rootella (trademark) mycorrhizae, N.13 + N.7 + N.14 + N.15 (BSST), N.16: Bacillus amyloliquefaciens velezensis MBI600, N.16 + cis-jasmone.
  13. The mixtures of claim 1 wherein component B) is selected from F.4:-Pyraclostrobin, F.10:-Fluopyram, F.11:-Fluxapyroxad, F.22:-Metalaxyl, F.31:-Flutriafol, F.35:-Mefentrifluconazole, F.37:-Prochloraz, F.38:-Fluquinconazole, F.39:-Triticonazole, F.40:-Imazalil, F.42:-Fludioxinil, F.43:-Thiabendazole, F.45:-Fluazinam, F.49:-Thiophanate-methyl, F.62:-Pencycuron, F.63:-Mancozeb, F.64:-thifluzamide, F.65:-chlorothalonil;
    In.1: Clothianidin, In.2: Thiamethoxam, In.4: Dinotefuran, In.6: Acetamiprid, In.20: Thiodicarb, In.23: Chlorantraniliprole, In.24: Cyantraniliprole, In.27: Fipronil, In.39: Abamectin, Bacillus species: N.12: Bacillus subtilis FMCH002.
  14. The mixtures of claim 1 wherein component B) is selected from clothianidin, broflanilide, chlorantraniliprole, fipronil; preferably clothianidin.
  15. The mixtures of any of claims 1 to 14, wherein compound I and compound II are present in a weight ratio of from 100:1 to 1:100, preferably 50:1 to 1:50, or 10:1 to 1:10 or 20:1 to 1:500, or 10:1 to 1:100, or 10:1 to 1:50, or 10:1 to 1:25, or 10:1 to 1:10.
  16. The mixtures of any of claims 1 to 15, which comprise a further compound II (component C), wherein the component C is selected from the same group of compounds as component B, with the proviso that component B and C are not identical.
  17. The mixtures of any of claims 1 to 15, which comprise two further compounds II (component C and D), wherein the components C and D are selected from the same group of compounds as component B, with the proviso that none of components B, C and D are identical.
  18. A composition comprising a pesticidal mixture according to any one of claims 1 to 17 and at least one inert liquid and/or solid carrier.
  19. A method for combating or controlling invertebrate pests or harmful pathogenic fungi, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of a pesticidal mixture according to any one of claims 1 to 17.
  20. A method for protecting growing plants or plant propagation materials from attack or infestation by invertebrate pests or harmful pathogenic fungi, which method comprises contacting a plant, a plant propagation material or soil or water in which the plant is growing, with a pesticidally effective amount of a pesticidal mixture according to any one of claims 1 to 17.
  21. A method for protection of plant propagation material comprising contacting the plant propagation material with the pesticidal mixture as defined in any of claims 1 to 17 in an amount of from 0.1 g to 10 kg per 100 kg of plant propagation material.

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