WO2016128239A1 - Pesticidal mixture comprising a pyrazole compound and a biopesticide - Google Patents

Pesticidal mixture comprising a pyrazole compound and a biopesticide Download PDF

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Publication number
WO2016128239A1
WO2016128239A1 PCT/EP2016/052030 EP2016052030W WO2016128239A1 WO 2016128239 A1 WO2016128239 A1 WO 2016128239A1 EP 2016052030 W EP2016052030 W EP 2016052030W WO 2016128239 A1 WO2016128239 A1 WO 2016128239A1
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lla
llla
spp
mixtures
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PCT/EP2016/052030
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French (fr)
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Ronald Wilhelm
Florent MAZUIR
Sebastian Soergel
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Basf Se
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • Pesticidal mixture comprising a pyrazole compound and a biopesticide
  • the present invention relates to mixtures of active compounds having synergistically enhanced action and to methods and uses comprising applying said mixtures.
  • Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests.
  • seed vitality - improving vitality of plant propagation material, also termed seed vitality
  • the present invention relates to pesticidal mixtures comprising as active components
  • R 1 is H, Ci-C 2 -alkyl, or Ci-C 2 -alkoxy-Ci-C 2 -alkyl;
  • R 2 is CH3, or halomethyl
  • R 3 is CN, d-Ce-alkyl, Ci-C 6 -haloalkyl, Ci-C 2 -alkoxy-Ci-C 2 -alkyl, C 2 -C 6 -alkenyl and C 2 -C 6 - alkynyl, C3-C6-cycloalkyl, Cs-Ce-cycloalkenyl, Ci-C6-alkoxy, wherein the C-atoms are unsubstituted, or partially or fully substituted by R a ,
  • R a is halogen, CN, Ci-C 2 -alkyl, Ci-C 2 -haloalkyl, Ci-C4-alkoxy, Ci-C 2 -haloalkoxy;
  • R 4 is Ci-C4-alkyl, or a group mentioned for R 3 ;
  • R 3 and R 4 may together form Cs-Ce-cycloalkyl, which is unsubstituted, or partially or fully substituted by R a ;
  • R 5 is H, or a group mentioned for R 4 ;
  • Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila,
  • Verticillium dahlia zucchini yellow mosaic virus (avirulent strain);
  • activator activity harpin protein, Reynoutria sachalinensis extract
  • Agrobacterium radiobacter Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp.
  • Helicoverpa zea nucleopolyhedrovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopliae, Metarhizium anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P.
  • promoting and/or yield enhancing activity Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium sp., Rhizobium leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti;
  • the present invention also relates to a seed treatment composition
  • a seed treatment composition comprising an auxiliary and a mixture of at least one active compound I and at least one biopesticide II as defined above.
  • the present invention also relates to the use of the mixture of at least one active compound I and at least one biopesticide II for protecting a plant, plant propagation material, or soil or water, in which the plants are growing, against the attack or infestation by invertebrate pests.
  • the present invention relates to the use of the mixture of at least one active compound I and at least one biopesticide II for protecting plant propagation material, preferably seeds, from soil insects and the seedlings' roots and shoots from soil and foliar insects, wherein the plant progagation material as e.g. the seeds are contacted with a pesticidally effective amount of the mixture before sowing and/or after pregermination.
  • the present invention further relates to a method for controlling invertebrate pests, which method comprises contacting the plant or the plant propagation material or the soil; the pests or their food supply, habitat or breeding grounds, with a pesticidally effective amount of the mixture of at least one active compound I and at least one biopesticide II.
  • the invention also provides seeds comprising the mixture of at least one active compound I and at least one biopesticide II.
  • mixture(s) of at least one active compound of formula I with at least one biopesticide II are herein referred to as "mixture(s) according to the invention” or “mixture(s) of the invention", wherein the compounds of formula I are understood to include their stereoisomers, salts, tautomers or N-oxides, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof.
  • the mixture according to the invention is a mixture of one active compound of formula I with one biopesticide II (binary mixture).
  • the mixture according to the invention is a mixture of one active compound of formula I with at least one biopesticide II.
  • composition(s) according to the invention or “composition(s) of the present invention” encompasses composition(s) comprising the mixtures of the invention, i.e. mixtures of the compounds of formula I with at least one biopesticide II for being used and/or applied in methods according to the invention as defined herein, wherein the compounds of formula I are understood to include their stereoisomers, salts, tautomers or N-oxides, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N- oxide thereof.
  • WO 2012/143317 and US 61/891437 and can be prepared by the methods described therein. These compounds are known to be useful for combating invertebrate pests.
  • WO2012/084670 and WO 2013/189801 describe pesticidal mixtures of compounds of formula I with fungicides or insecticides. However, mixtures of compounds of formula I with
  • biopesticides have not been described previously.
  • compound(s) of formula I or “compound(s) according to the invention” comprises the compound(s) as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof.
  • compound(s) of the present invention is to be understood as equivalent to the term “compound(s) according to the invention”, therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof.
  • the compounds of the present invention may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers.
  • the invention encompasses both the pure enantiomers or pure diastereomers of the compounds of the present invention, and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compounds of the present invention or their mixtures.
  • Suitable compounds of the formula of the present invention also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof.
  • Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond, nitrogen-sulfur double bond or amide group.
  • stereoisomer(s) 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).
  • N-oxide includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.
  • N-oxides of compounds of the present invention can in particular be prepared by oxidizing the ring nitrogen atom(s) of the pyridazine ring and/or the pyrazole ring with a suitable oxidizing agent, such as peroxo carboxylic acids or other peroxides.
  • a suitable oxidizing agent such as peroxo carboxylic acids or other peroxides.
  • Salts of the compounds of the present invention are preferably agriculturally acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid if the compound of the present invention has a basic functionality or by reacting the compound with a suitable base if the compound of the present invention has an acidic functionality.
  • suitable "agriculturally useful salts” or “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 present 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 (NhV) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci- C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-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 Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Preferred compounds of the present invention are compounds of formula I or a stereoisomer, N-oxide or salt thereof, wherein the salt is an agriculturally acceptable salt.
  • the compounds of of the formula I may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities.
  • the present 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.
  • Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, microbial and biochemical pesticides:
  • Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classified as microbial pesticides, even though they are multi-cellular.
  • Biochemical pesticides are naturally occurring substances or or structurally-similar and functionally identical to a naturally-occurring substance and extracts from biological sources that control pests or provide other crop protection uses as defined below, but have non-toxic mode of actions (such as growth or developmental regulation, attractents, repellents or defence activators (e.g. induced resistance) and are relatively non-toxic to mammals.
  • the biopesticides from group L1 ) and/or L2) may also have insecticidal, acaricidal, molluscidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity.
  • the biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity.
  • the biopesticides from group L5) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
  • plantarum QST-713 isolated from peach orchard in 1995 in California, U.S.A. (NRRL B-21661 ; e. g. Serenade® MAX from Bayer Crop Science LP, USA), B. amyloliquefaciens spp. plantarum TJ1000 isolated in 1992 in South Dakoda, U.S.A. (also called 1 BE; ATCC BAA-390; CA
  • pumilus INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tracheiphila (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumilus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumilus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL
  • B-30087 B-30087; e. g. Sonata® or Ballad® Plus from Bayer Crop Science LP, USA
  • B. simplex ABU 288 NRRL B-50304; US 8,445,255
  • B. subtilis FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA-1 1857; System. Appl. Microbiol. 27, 372-379, 2004; US 2010/0260735; WO 201 1/109395);
  • Contans® WG, Intercept® WG from Bayer CropScience AG, Germany Contans® WG, Intercept® WG from Bayer CropScience AG, Germany
  • harpin (alpha- beta) protein Science 257, 85-88, 1992; e. g. MessengerTM or HARP-N-Tek from Plant Health Care pic, U.K.
  • HearNPV Helicoverpa armigera nucleopolyhedrovirus
  • HSSNPV capsid nucleopolyhedrovirus
  • Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditis bacteriophora (e. g. Nemasys® G from BASF
  • ClarivaTM PN from Syngenta Crop Protection, LLC, USA
  • Penicillium bilaiae also called P. bilaii
  • ATCC 18309 ATCC 74319
  • ATCC 20851 and/or ATCC 22348 ATCC 743148
  • ATCC 743178 ATCC 743178
  • T. harzianum -22 also called KRL-AG2 (ATCC 20847; BioControl 57, 687-696, 2012; e. g. Plantshield® from BioWorks Inc., USA or SabrExTM from Advanced Biological Marketing Inc., Van Wert, OH, USA).
  • biopesticides which have been deposited under deposition numbers mentioned herein (the prefices such as ATCC or DSM refer to the acronym of the respective culture collection, for details see e. g. here: http://www. wfcc.info/ccinfo/collection/by_acronym/), are referred to in literature, registered and/or are commercially available: mixtures of Aureobasidium pu/lu/ans DSM 14940 and DSM 14941 isolated in 1989 in Konstanz, Germany (e. g.
  • plantarum QST-713 isolated from peach orchard in 1995 in California, U.S.A. (NRRL B-21661 ; e. g. Serenade® MAX from Bayer Crop Science LP, USA), B. amyloliquefaciens spp. plantarum TJ1000 isolated in 1992 in South Dakoda, U.S.A. (also called 1 BE; ATCC BAA-390; CA
  • pumilus INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tracheiphila (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumilus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumilus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL
  • B-30087 B-30087; e. g. Sonata® or Ballad® Plus from Bayer Crop Science LP, USA
  • B. simplex ABU 288 NRRL B-50304; US 8,445,255
  • B. subtilis FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA-1 1857; System. Appl. Microbiol. 27, 372-379, 2004; US 2010/0260735; WO 201 1/109395);
  • Contans® WG, Intercept® WG from Bayer CropScience AG, Germany Contans® WG, Intercept® WG from Bayer CropScience AG, Germany
  • harpin (alpha- beta) protein Science 257, 85-88, 1992; e. g. MessengerTM or HARP-N-Tek from Plant Health Care pic, U.K.
  • HearNPV Helicoverpa armigera nucleopolyhedrovirus
  • HSSNPV capsid nucleopolyhedrovirus
  • Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditis bacteriophora (e. g. Nemasys® G from BASF
  • ClarivaTM PN from Syngenta Crop Protection, LLC, USA
  • Penicillium bilaiae also called P. bilaii
  • ATCC 18309 ATCC 74319
  • ATCC 20851 and/or ATCC 22348 ATCC 743148
  • ATCC 743178 ATCC 743178
  • T. harzianum -22 also called KRL-AG2 (ATCC 20847; BioControl 57, 687-696, 2012; e. g. Plantshield® from BioWorks Inc., USA or SabrExTM from Advanced Biological Marketing Inc., Van Wert, OH, USA).
  • Preferred biopesticides on strain level are selected from the following groups L1 ) to L5):
  • Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Aureobasidium pullulans DSM 14940 and DSM 14941 (L1.1 ), Bacillus amy/o- liquefaciens AP-188 (L.1.2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B. amylo- liquefaciens ssp. plantarum FZB24 (L.1.4), B. amyloliquefaciens ssp. plantarum FZB42 (L.1.5), B. amyloliquefaciens ssp.
  • pum/ius QSJ 2808 (L.1.13), B. simplex ABU 288 (L.1.14), B. subtilis FEM (L.1.15), Coniothyrium minitans CON/M/91-08 (L.1.16), Metschnikowia fructicola NRRL Y-30752 (L.1.17), Penicillium bilaiae ATCC 22348 (L.1.19), P. bilaiae ATCC 20851 (L.1.20), Penicillium bilaiae ATCC 18309 (L.1.21 ), Streptomyces microflavus NRRL B-50550 (L.1.22), T. harzianum T-22 (L.1.24);
  • harpin protein L.2.1
  • Reynoutria sachalinensis extract L.2.2
  • Bacillus firmus ⁇ - ⁇ 82 (L.3.1 ); B. thuringiensis ssp. aizawai NSX ⁇ - ⁇ 8 l (L.3.2), B. t. ssp. kurstaki ABTS-351 (L.3.3), B. t. ssp. tenebrionis NB-176-1 (L.3.5), Beauveria bassiana GHA (L.3.6), B. bassiana SWA (L.3.7), Burkholderia sp. A396 (L.3.9), Helicoverpa
  • HearNPV nucleopolyhedrovirus
  • HzNPV nucleopolyhedrovirus
  • HzSNPV Helicoverpa zea single capsid nucleopolyhedrovirus
  • L.3.13 Heterohabditis bacteriophora
  • /ss /s fumosorosea Apopka-97 L.3.14
  • nematicidal activity cis-jasmone (L.4.1 ), methyl jasmonate (L.4.2), Quillay extract
  • L1 Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Aureobasidium pullulans DSM 14940 and DSM 14941 (L1.1 ), Bacillus amyloliquefaciens AP-188 (L.1 .2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B. amyloliquefaciens ssp. plantarum FZB24 (L.1.4), B. amyloliquefaciens ssp. plantarum FZB42 (L.1 .5), z5. amyloliquefaciens ssp.
  • harpin protein L.2.1
  • Reynoutria sachalinensis extract L.2.2
  • Bac/i/us firmus ⁇ A 582 (L.3.1 ); B. thuringiensis ssp. a/ ai/1 ⁇ 23/ ' ABTS-1857 (L.3.2), z5. /. ssp. yre sA/ ABTS-351 (L.3.3), B. t. ssp. tenebrionis NB-176-1 (L.3.5), Beauveria bassiana GHA (L.3.6), /?. bassiana SWA (L.3.7), Burkholderia sp.
  • A396 (L.3.9), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (L.3.10), Helicoverpa zea nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.1 1), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (L.3.12), Heterohabditis bacteriophora A S), Isaria fumosorosea Apopka- 97 (L.3.14), Metarhizium anisop/iae var.
  • anisop/iae F52 (L.3.15), Paeci/omyces ///acinus 251 (L.3.16), Pasteur/a nishizawae Pn (L.3.17), Steinernema carpocapsae (L.3.18), 5.
  • nematicidal activity cis-jasmone (L.4.1 ), methyl jasmonate (L.4.2), Quillay extract (L.4.3).
  • mixtures comprising as pesticide II (component 2) a biopesticide selected from the groups L1 ), L3) and L5), preferably selected from strains denoted above as (L.1.2), (L.1.3), (L.1.4), (L.1 .5), (L.1 .6), (L.1 .7), (L.1.8), (L.1.10), (L.1 .1 1 ), (L.1.12), (L.1 .13), (L.1.14), (L.1.15), (L.1.17), (L.1 .18), (L.1.19), (L.1 .20), (L.1.21 ), (L.3.1 ); (L.3.9), (L.3.16), (L.3.17), (L.5.1 ), (L.5.2), (L.5.3), (L.5.4), (L.5.5), (L.5.6), (L.5.7), (L.5.8); (L.4.2), and (L.4.1 ); even more preferably selected from (L.1.2), (L
  • mixtures comprising as pesticide II (component 2) a biopesticide selected from the groups L1 ), L3) and L5), preferably selected from strains denoted above as (L1.1 ), (L.1 .2), (L.1 .3), (L.1 .6), (L.1 .7), (L.1 .9), (L.1.1 1 ), (L.1.12), (L.1.13), (L.1.14), (L.1.15), (L.1.17), (L.1.18), (L.1.22), (L.1 .23), (L.1.24), (L.2.2); (L.3.2), (L.3.3), (L.3.4), (L.3.5), (L.3.6), (L.3.7), (L.3.8), (L.3.10), (L.3.1 1 ), (L.3.12), (L.3.13), (L.3.14), (L.3.15), (L.3.18), (L.3.19); (L.4.2), even more preferably
  • the mixtures of the invention embrace not only the isolated, pure cultures of the respective microorganisms as defined herein, but also its cell-free extract having pesticidal activity, preferably a ketone-based extract, its suspensions in a whole broth culture or as a metabolite-containing supernatant or a purified metabolite obtained from a whole broth culture of the microorganism or microorganism strain.
  • “Whole broth culture” refers to a liquid culture containing both cells and media.
  • Supernatant or “culture medium” refers to the liquid broth remaining when cells grown in broth are removed by centrifugation, filtration, sedimentation, or other means well known in the art.
  • metabolite refers to any compound, substance or byproduct (including but not limited to small molecule secondary metabolites, polyketides, fatty acid synthase products, non- ribosomal peptides, ribosomal peptides, proteins and enzymes) produced by a microorganism (such as fungi and bacteria) that has pesticidal activity or improves plant growth, water use efficiency of the plant, plant health, plant appearance, or the population of beneficial microorganisms in the soil around the plant activity.
  • mutant refers to a microorganism, obtained by direct mutant selection but also includes microorganisms that have been further mutagenized or otherwise manipulated (e. g., via the introduction of a plasmid).
  • embodiments include mutants, variants, and or derivatives of the respective microorganism, both naturally occurring and artificially induced mutants.
  • mutants may be induced by subjecting the microorganism to known mutagens, such as N-methyl-nitrosoguanidine, using conventional methods.
  • mutagens such as N-methyl-nitrosoguanidine
  • R 1 is H, CH3, C2H5, or CH2OCH3, preferably CH3, or C2H5.
  • R 2 is CH3.
  • R 3 is Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C6-cycloalkyl, wherein the C-atoms may be unsubstituted, or partially or fully substituted by halogen, or CN.
  • R 3 is CH 3 , C 2 H 5 , CH(CH 3 ) 2 , CH2CH2CH3, CF 3 , CHFCH3, cyclopropyl, wherein the ring is substituted by halogen, or CN.
  • R 3 is CH 3 , CH(CH 3 ) 2 , CF 3 , CHFCH3, 1 -CN-c-C 3 H 4 .
  • R 4 is Ci-C4-alkyl, preferably CH3.
  • R 3 and R 4 together form Cs-Ce-cycloalkyl, wherein the C-atoms may be unsubstituted, or partially or fully substituted by halogen, or CN.
  • R 5 is H.
  • R 5 is H, and R 4 is CH3.
  • R 1 is CH 3 or C 2 H 5
  • R 2 is CH 3
  • R 5 is H
  • R 4 is CH 3
  • R 3 is selected from CH 3 , CH(CH 3 ) 2 , CF 3 , CHFCH3, and 1 -CN-c-C 3 H 4 .
  • the compound of formula I is a compound of formula IA as depicted below, wherein R 2 is CH3 and
  • R 1 is H, CH3, C2H5, or
  • R 3 is CH3, C2H5, CH(CH3)2, CH2CH2CH3, CF3, CHFCH3, cyclopropyl, wherein the ring is substituted by halogen, or CN, and that R 4 is Ci-C4-alkyl, or that R 3 and R 4 together form Cs-Ce-cycloalkyl, which is unsubstituted, or partially or fully substituted by halogen, or CN.
  • Particularly preferred compounds of formula I are compounds of formula IA, wherein the variables R 1 , R 3 , and R 4 correspond to one row of table I below. Said compounds are referred to as compounds 1-1 to 1-18 in accordance with each row of table I.
  • the pesticidal mixtures of the invention comprise a component 2), which is a biopesticide II, which is selected from the groups L1 to L5 as defined above. Preferred biopesticides II are defined hereinafter.
  • biopesticides II which may be selected as component 2) of the mixtures of the invention, are to be understood as preferred on their own as well as preferably in combination with the preferred embodiments of the compounds of formula I, i.e. component 1 ) of the mixture of the invention, and, where applicable, as well as concerning the uses and methods according to the invention and the compositions according to the invention.
  • biopesticide II component 2
  • a biopesticide selected from group L1 preferably selected from Bacillus amyloliquefaciens herein even more preferably from strains AP-136, AP-188, AP-218, AP-219, AP-295, IN937a, IT-45; B.
  • amyloliquefaciens ssp. plantarum (formerly called B. subtilis or B. subtilis spp.
  • amyloliquefaciens herein even more preferably from strains MBI600, D747, FZB24, FZB42, GB03, QST-713 and TJ1000; B. mojavensis AP-209; B. pumilus herein even more preferably from strains GHA 180, INR-7, and QST 2808; B. simplex here ' m more preferably strain ABU 288; B. so/isa/si herein more preferably strain AP-217; B.
  • subtilis herein even more preferably selected from strains CX-9060, FB17 and GB07; Muscodor a/bus herein more preferably strains QST 20799 and SA-13; Paenibacillus polymyxa herein more preferably strain PKB1 ,
  • Penicillium bilaiae herein more preferably strains ATCC 22348, ATCC 20581 and ATCC 18309; Pseudomonas fluorescens herein more preferably strain A506; Sphaerodes mycoparasitica herein more preferably strain SMCD2220; ; Trichoderma harzianum herein more preferably strain T-22; Trichoderma virens herein more preferably strais GI-3 and G-41.
  • biopesticide II component 2
  • a biopesticide selected from group L1 even more preferably selected from B. amyloliquefaciens AP-188, B. amylolique faciens ssp. plantarum MBI600, B. amyloliquefaciens ssp. plantarum QST -1 ?>, B. pumilus INR-7, /?. pumilus QST 2808, /?. simplex ABU 288, and /?. si//W/s FB17.
  • the at least one biopesticide II is Bacillus amyloliquefaciens ssp. plantarum MBI600. These mixtures are particularly suitable in soybean.
  • the at least one biopesticide II is B. pumilus INR-7. These mixtures are particularly suitable in soybean and corn.
  • the at least one biopesticide II is Bacillus simplex, preferably B. simplex ABU 288. These mixtures are particularly suitable in soybean and corn.
  • the at least one biopesticide II is Bacillus subtilis, preferably B. subtilis strain FB17.
  • the at least one biopesticide II is selected from Bacillus amyloliquefaciens AP-136, B. amyloliquefaciens AP-188, B.
  • pumilus INR-7 z5. pumilus QST 2808, z5. pumilus GHA 180, z5. simplex ABU 288, z5. solisalsi AP-217, z5. subti/is CX-9060, B. subtilis FB17 and z5. s ubti/is GB07.
  • These mixtures are particularly suitable in soybean and corn, in particular for seed treatment.
  • the at least one pesticide II is selected from Streptomyces spp., preferably from 5. griseoviridis, S. lydicus and 5. violaceusniger, in particular from strains 5. griseoviridis ⁇ & ⁇ , S. iydicus ⁇ NYEC 108, 5. violaceusniger XL-2 and 5. vio/aceusnigerYCED- 9.
  • the at least one biopesticide II is selected from the following fungi Coniothyrium minitans CON/M/91-08, 7! harzianum T-22, 7! i//re/7s GI-3, 7! wjre/7s GL-21 , 7! wjre/7s G-41. These mixtures are particularly suitable for seed and/or soil treatment.
  • the at least one biopesticide II is selected from Pseudo- monas spp., preferably selected from P. chloraphis herein more preferably strain MA 342 and Pseudomonas sp. DSM 13134; P. fluorescens herein more preferably selected from strains A506, WCS 374 and Pf-5; and P. put/da herein more preferably strain ATCC 202153.
  • the present invention also relates to mixtures wherein the at least one biopesticide II is selected from the fungal genus Trichoderma, preferably from the strains T. asperellum T34, T. asperellum SKT-1 , T. asperellum ICC 012, T. asperellum ⁇ V ⁇ , T. atroviride LC52, T. atroviride CNCM 1-1237, T. gamsii ⁇ CC 080, T. harmatum JH 382, T. harzianum -22, T. harzianum T-35, T. harzianum T-39, T. harzianum T-315; mixture of T. harzianum ICC012 and T.
  • the present invention also relates to mixtures wherein the at least one biopesticide II is selected from the fungal species Muscodor a/bus preferably from the strains SA-13 and QST 20799, which are particularly suiable for soil and seed treatment against soil-borne pathogens and/or nematodes.
  • biopesticide II component 2
  • component 3 a biopesticide selected from group L3
  • Bacillus firmus herein preferably strain 1-1582
  • Beauveria bass/ana herein preferably selected from strains GHA, H123, and DSM 12256;
  • biopesticide II component 2 a biopesticide selected from group L3
  • component 2 a biopesticide selected from group L3
  • B. bass/ana DSM 12256 Metarhizium anisopliae var. acr/dum ⁇ M ⁇ 330189
  • M. anisopliae FI-985 M. anisopliae FI-1045
  • P. lilacinus 251 Paenibacillus popilliae Dutky-1940, P. popilliae KLN 3 and P. popilliae Dutky 1 .
  • the at least one biopesticide II is Beauveria brongniartii. According to a further embodiment, the at least one biopesticide II is Metarhizium anisopliae or M. anisopliae var. acridium, preferably selected from M. anisopliae FI-1045, M. anisopliae F52, M. anisopliae var. acr/dum strains FI-985 and IMI 330189; in particular strain IMI 330189. These mixtures are particularly suitable for control of arthropod pests in soybean and corn.
  • the at least one biopesticide II is Paecilomyces fumoso- roseus, preferably strain FE 9901 especially for white fly control.
  • the at least one biopesticide II is selected from Nomuraea rileyi, preferably strains SA86101 , GU87401 , SR86151 , CG128 and VA9101 ; and P. lilacinus, preferably strains 251 , DSM 15169 or BCP2, in particular BCP2, which strains especially control the growth of plant-pathogenic nematodes.
  • the at least one biopesticide II is Bacillus firmus, preferably spores of strain CNCM 1-1582, preferably useful for seed treatment of cereals, soybean, cotton, sugarbeets and corn against nematodes and insects.
  • the at least one biopesticide II is Pasteur/a nishizawae, preferably spores of strain Pn1 , preferably useful for seed treatment of cereals, soybean, cotton, sugarbeets and corn against nematodes and insects.
  • the at least one biopesticide II is Flavobacterium sp., preferably spores of strain H492, preferably useful for seed treatment of cereals, soybean, cotton, sugarbeets and corn against nematodes and insects.
  • the at least one biopesticide II is Bacillus cereus, preferably spores of CNCM 1-1562, preferably useful for seed treatment of soybean, cotton, cereals, and corn against nematodes and insects.
  • the at least one biopesticide II is Burkholderia sp., preferably strain A396, preferably useful for seed treatment of soybean, cotton, cereals, and corn.
  • the at least one biopesticide II is Paecilomyces lilacinus 251 , preferably useful for seed treatment of soybean, cotton, cereals, and corn.
  • the at least one biopesticide II is a mixture of spores of B. firmus and B. cereus, preferably mixtures spores of above mentioned strains CNCM 1-1582 and CNCM 1-1562, preferably useful for seed treatment of soybean, cotton, cereals, and corn against nematodes and insects.
  • the at least one pesticide II is selected from Bacillus firmus CNCM 1-1582, Paecilomyces lilacinus 251 , Pasteuria nishizawa Pn1 and Burkholderia sp. A396 having nematicidal, acaricidal and/or insecticidal activity. These mixtures are particularly suitable in soybean, cotton, cereals, and corn, in particular for seed treatment.
  • biopesticide II component 2
  • component 2 a biopesticide selected from group L4
  • methyl jasmonate preferably methyl jasmonate
  • biopesticide II component 2
  • a biopesticide selected from group L5 preferably selected from Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp. (Arachis), Bradyrhizobium sp.
  • leguminosarum bv. phaseo/i R. I. bv. trifolii
  • R. I. bv. viciae R. I. bv. viciae
  • Sinorhizobium meliloti
  • biopesticide II component 2
  • component 2 a biopesticide selected from group L5) selected from Azospirillum amazonense SpY2, A. brasilense XOH, A. brasilense Cd, A. lipoferum Sp31 , Bradyrhizobium sp. (Vigna) PNL1 , B. japonicum TA-1 1 ,
  • leguminosarum b . phaseoli RG-B10 R. I. bv. viciae P1 NP3Cst, R. I. bv. viciae R G -P2, R. I. bv. trifolii RP1 13-7, R. I. bv. viciae SU303, R. I. bv. viciae WSM1455, R. tropic/ SEMA 4077, R. tropic/ PRF 81 and Sinorhizobium meliloti, even more preferably selected from Bradyrhizobium sp. (Vigna) PNL1 , B. japonicum TA-1 1.
  • the present invention also relates to mixtures, wherein the at least one biopesticide II is selected from Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense and A.
  • halopraeferens more preferably from A. brasilense. These are particularly suitable in soybean, especially as seed treatment.
  • component 2) i.e. the biopesticide II, of the mixtures of the invention is selected from Azospirillum amazonense, Azospirillum brasilense, Azospirillum lipoferum, Azospirillum irakense, Azospirillum halopraeferens, Bradyrhizobium spp., Bradyrhizobium sp. (Arachis), Bradyrhizobium sp. (Vigna), Bradyrhizobium elkanii, Bradyrhizobium japonicum,
  • Bradyrhizobium liaoningense Bradyrhizobium lupini, Dei ft/a ac/dovorans, Glomus intraradices, Mesorhizobium sp., Mesorhizobium ciceri, Mesorhizobium huakii, Mesorhizobium lot/,
  • Rhizobium leguminosarum bv. phaseoli Rhizobium leguminosarum bv. trifolii, Rhizobium leguminosarum bv. viciae, Rhizobium tropic/ ' , Sinorhizobium meliloti, Bacillus altitudinis, Bacillus amyloliquefaciens, Bacillus amyloliquefaciens ssp.
  • component 2) i.e. the biopesticide II, of the mixtures of the invention is selected from Azospirillum amazonense SpY2, Azospirillum brasilense AZ39 also called Az 39, Azospirillum brasilense Cd, Azospirillum brasilense Sp 245, Azospirillum brasilense XOH, Azospirillum lipoferum Sp31 , Bradyrhizobium elkanii J- 30 , Bradyrhizobium elkanii U-1302, Bradyrhizobium elkanii ⁇ JSOfk 3254, Bradyrhizobium elkanii USDA 76,
  • Bradyrhizobium elkanii S DA 94 Bradyrhizobium japonicum G49, Bradyrhizobium japonicum SEMIA 566, Bradyrhizobium japonicum ! ⁇ -1 1 (TA1 1 NOD+), Bradyrhizobium japonicum USDA 1 10, Bradyrhizobium japonicum USDA 121 , Bradyrhizobium japonicum USDA 3,
  • Bradyrhizobium japonicum USDA 31 Bradyrhizobium japonicum USDA 76, Bradyrhizobium sp. (Arachis) CB1015, Bradyrhizobium sp. (Arachis) SEMIA 6144, Bradyrhizobium sp. (Arachis) SEMIA 6462, Bradyrhizobium sp. (Arachis) SEMIA 6464, Bradyrhizobium sp. (Vigna) PNL1 , Mesorhizobium sp. WSM1497, Rhizobium leguminosarum by. phaseoli RG-B 0, Rhizobium leguminosarum by.
  • Rhizobium leguminosarum bv . wc/ae P1 NP3Cst also referred to as 1435
  • Rhizobium leguminosarum bv. wc/ae RG-P2 also called P2
  • Rhizobium leguminosarum bv. wc/ae SU303 Rhizobium leguminosarum bv.
  • amyloliquefaciens AP-219 Bacillus amyloliquefaciens AP-295, Bacillus amyloliquefaciens ssp. plantarum ⁇ 7 ⁇ 7, Bacillus amyloliquefaciens ssp. plantarum FZB24 also called SB3651 , Bacillus amyloliquefaciens ssp. plantarum FZB42, Bacillus amyloliquefaciens ssp. plantarum GB03 also called GB03 formerly z5. subtilis, Bacillus amyloliquefaciens ssp. plantarum MBI600 also referred to as 1430, formerly B.
  • component 2) i.e. the biopesticide II, of the mixtures of the invention is selected from
  • Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila,
  • activator activity harpin protein, Reynoutria sachalinensis extract
  • Agrobacterium radiobacter Bacillus cereus, B. firmus, Burkholderia sp.,
  • nematicidal activity cis-jasmone, methyl jasmonate, jasmonic acid or salts or derivatives thereof;
  • component 2) i.e. the biopesticide II, of the mixtures of the invention is selected from the group L1 , i.e.
  • microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B.
  • ⁇ '/ate also named Gliocladium eaten ulatum
  • Gliocladium roseum also named Lysobacter antibioticus, L enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus polymyxa, Pantoea vagans, Penicillium bilaiae, P.
  • component 2) i.e. the biopesticide I I, of the mixtures of the invention is selected from Bacillus amyloliquefaciens, Bacillus pumilus, Bacillus simplex, and Bacillus subtilis, in particular from the strains Bacillus amyloliquefaciens MBI600, B.
  • the biopesticide II of the mixtures of the invention is Bacillus pumilus, preferably spores of strain INR-7.
  • the biopesticide II of the mixtures of the invention is Bacillus simplex, preferably spores of strain ABU 288.
  • the biopesticide II of the mixtures of the invention is Bacillus subtilis, preferably spores of strain FB17.
  • component 2) i.e. the biopesticide II, of the mixture of the invention is Penicillium steckii, preferably Penicillium steckii strain IBWF104-06 as deposited with DSMZ under the deposit number DSM 27859. Strain IBWF104-06 was determined to have potent antifungal activity, in particular, against infestion with plant pathogens including
  • component 2) i.e. the biopesticide II, of the mixtures of the invention is selected from the group L2, i.e. biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract.
  • the biopesticide II of the mixture of the invention is harpin protein (alpha-beta).
  • component 2), i.e. the biopesticide II, of the mixtures of the invention is selected from the group L4, i.e. biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: cis-jasmone, methyl jasmonate, jasmonic acid or salts or derivatives thereof.
  • the biopesticide II of the mixtures of the invention is cis-jasmone.
  • the biopesticide II of the mixture of the invention is methyl jasmonate.
  • the biopesticide II of the mixture of the invention is jasmonic acid or a salt or derivative thereof.
  • component 2), i.e. the biopesticide II, of the mixtures of the invention is selected from the group L3, i.e. microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, Burkholderia sp., Chromobacterium subtsugae, Flavobacterium sp., Paecilomyces
  • component 2) i.e. the biopesticide I I, of the mixtures of the invention is selected from Bacillus firmus, Pasteur/a nishazawa sp., Flavobacterium sp., Paecilomyces lilacinus, and Burkholderia sp, in particular from the strains Burkholderia sp. A396, Paecilomyces lilacinus 251 , Bacillus firmus CNCM 1-1582, Pasteur/a nishizawae - Pn1 , and Flavobacterium sp. H492.
  • component 2) i.e. the biopesticide II, of the mixtures of the invention is selected from Bacillus firmus, Pasteur/a nishizawa, and Flavobacterium sp., in particular from the strains Bacillus firmus CNCM 1-1582, Pasteur/a nishizawae Pn1 , and Flavobacterium sp. H492.
  • the biopesticide II of the mixtures of the invention is Bacillus cereus, preferably spores of strain CNCM 1-1562.
  • the biopesticide II of the mixtures of the invention is Burkholderia sp., preferably strain A396.
  • the biopesticide II of the mixtures of the invention is Paecilomyces lilacinus, preferably strain 251 , DSM 15169 or BCP2, particularly preferably strain 251 .
  • the biopesticide II of the mixtures of the invention is Bacillus firmus, preferably spores of strain CNCM 1-1582; e.g. VOTiVO® from Bayer CropScience LP, USA, which is suitable for nematode control.
  • the biopesticide II of the mixtures of the invention is Pasteur/a nishizawae, preferably spores of strain Pn1 , e.g. Clariva® PN from Syngenta Crop Protection, LLC, USA, which is suitable for nematode control.
  • the biopesticide II of the mixtures of the invention is Flavobacterium sp., preferably spores of strain H492, e.g. MBI-302 from Marrone Bio Innovations, USA, which is suitable for nematode control.
  • particularly preferred biopesticides II may be selected from the following biopesticides 11-1 to 11-14 in accordance with each row of table II, of which biopesticides 11-12, I ll s, and 11-14 are particularly preferred.
  • particularly preferred strains of biopesticides II may be selected from the following biopesticide strains lla-1 to lla-1 1 in accordance with each row of table I la, of which the biopesticide strains lla-9, lla-10, and lla-1 1 are particularly preferred.
  • the mixtures A-1 to A-252 are preferably binary mixtures.
  • the mixtures A-199 to A-252 are preferred, e.g. the mixtures A-199 to A- 216, or A-217 to A-234, or A-235 to A-252 may be particularly preferred.
  • the mixtures B-1 to B-198 are preferably binary mixtures.
  • the mixtures B-145 to B-198 are preferred, e.g. the mixtures B-145 to B- 162, or B-163 to B-180, or B-181 to B-198 may be particularly preferred.
  • the solid material (dry matter) of the biopesticides (with the exception of oils such as 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 such as 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 calclulate the total weight of the respective active component with the following equation that 1 x 10 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 (entomopathogenic) nematode biopesticides, such as
  • component 1 ) and component 2) of the mixtures of the invention are present in synergistically effective amounts.
  • component 1) and component 2) of the mixtures of the invention are present in a total weight ratio of from 100:1 to 1 :100, wherein the total weight of component 2) is based on the amount of the solid material (dry mater) of component 2).
  • the weight ratio of the component 1 ) and the component 2) generally depends from the properties of the active components used, usually it is in the range of from 1:10,000 to 10,000:1, often it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1, even more preferably in the range of from 1:4 to 4:1 and in particular in the range of from 1:2 to 2:1.
  • the weight ratio of the component 1) and the component 2) usually is in the range of from 1000:1 to 1:1, often in the range of from 100: 1 to 1:1, regularly in the range of from 50:1 to 1:1, preferably in the range of from 20:1 to 1:1, more preferably in the range of from 10:1 to 1:1, even more preferably in the range of from 4:1 to 1:1 and in particular in the range of from 2:1 to 1:1.
  • the weight ratio of the component 1) and the component 2) usually is in the range of from 20,000:1 to 1:10, often in the range of from 10,000:1 to 1:1, regularly in the range of from 5,000:1 to 5:1, preferably in the range of from 5,000:1 to 10:1, more preferably in the range of from 2,000:1 to 30:1, even more preferably in the range of from 2,000:1 to 100:1 and in particular in the range of from 1,000:1 to 100:1.
  • the weight ratio of the component 1) and the component 2) usually is in the range of from 1:1 to 1:1000, often in the range of from 1:1 to 1:100, regularly in the range of from 1:1 to 1:50, preferably in the range of from 1:1 to 1:20, more preferably in the range of from 1:1 to 1:10, even more preferably in the range of from 1:1 to 1:4 and in particular in the range of from 1:1 to 1:2.
  • the weight ratio of the component 1) and the component 2) usually is in the range of from 10:1 to 1:20,000, often in the range of from 1:1 to 1:10,000, regularly in the range of from 1:5 to 1:5,000, preferably in the range of from 1:10 to 1:5,000, more preferably in the range of from 1:30 to 1:2,000, even more preferably in the range of from 1 : 100 to 1 :2,000 to and in particular in the range of from 1 : 100 to 1:1,000.
  • the weight ratio of component 1) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 : 100 to 100:1, regularly in the range of from 1 :50 to 50: 1 , preferably in the range of from 1 :20 to 20: 1 , more preferably in the range of from 1 : 10 to 10:1 and in particular in the range of from 1:4 to 4:1, and the weight ratio of component 1) and component 3) usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1 :4 to 4: 1.
  • any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the component 1).
  • the application rates preferably range from about 1 x 10 6 to 5 x 10 15 (or more) CFU/ha, preferably from about 1 x 10 8 to about 1 x 10 13 CFU/ha, and even more preferably from about 1 x 10 9 to about 1 x 10 12 CFU/ha.
  • (entomopathogenic) nematodes as microbial pesticides (e. g.
  • the application rates preferably range inform about 1 x 10 5 to 1 x 10 12 (or more), more preferably from 1 x 10 8 to 1 x 10 11 , even more preferably from 5 x 10 8 to 1 x 10 10 individuals (e. g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha.
  • the application rates with respect to plant propagation material preferably range from about 1 x 10 6 to 1 x 10 12 (or more) CFU/seed.
  • the concentration is about 1 x 10 6 to about 1 x 10 9 CFU/seed.
  • the application rates with respect to plant propagation material also preferably range from about 1 x 10 7 to 1 x 10 14 (or more) CFU per 100 kg of seed, preferably from 1 x 10 9 to about 1 x 10 12 CFU per 100 kg of seed.
  • the mixtures of the invention in particular the mixtures A-1 to A-108 or B-
  • active component 3 a further active compound III, which is selected from insecticides or fungicides.
  • insecticides which are hereinafter described by common names, are commercially available and may be found in The Pesticide Manual, 16th Edition, C. MacBean, British Crop
  • the mixtures of the invention further comprise as active component 3) a further active compound III, which is an insecticide, wherein said insecticide is selected from the group consisting of fipronil, clothianidin, thiamethoxam, acetamiprid, dinotefuran, imidacloprid, thiacloprid, sulfoxaflor, methiocarb, tefluthrin, bifenthrin, cypermethrin, alphacypermethrin, spinosad, cyantraniliprole, chlorantraniliprole, triflumezopyrim, flupyradifurone, abamectin, thiodicarb, tetraniliprole, tioxazafen, and broflanilide.
  • insecticide is selected from the group consisting of fipronil, clothianidin, thiamethoxam, acetamiprid, dinotefuran, imid
  • the mixtures of the invention further comprise as active component 3) a further active compound III, which is a fungicide, wherein said fungicide is selected from the group consisting of azoxstrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, sedaxane, penthiopyrad, penflufen, fluopyram, fluxapyroxad, boscalid, oxathiapiprolin, metalaxyl, metalaxyl-M, ethaboxam, dimethomorph, cyproconazole, difenoconazole, prothioconazole, flutriafol, thiabendazole, ipconazole, tebuconazole, triadimenol, prochloraz, fluquinconazole, triticonazole, fludioxonil, carboxin, silthiofarm, ziram, thiram, carbendazim,
  • the active compound III is an insecticide
  • said insecticide is preferably selected from the insecticides as defined in the following table Ilia.
  • the insecticides as listed in table Ilia are in the following referred to as insecticides llla-1 to ll la-22.
  • the active compound III is a fungicide
  • said fungicide is preferably selected from the fungicides as defined in the following table lllb.
  • the fungicides as listed in table lllb are in the following referred to as fungicides lllb-1 to lllb-36.
  • the present invention relates to mixtures, which comprise at least one compound of formula I, which is selected from the compounds 1-1 to 1-18, as component 1 ), and at least one biopesticide II, which is selected from the biopesticides 11-1 to 11-14, in particular from the biopesticide strains lla-1 to lla-1 1 , and at least one further active compound III, which may be selected from the insecticides llla-1 to llla-23, or the fungicides lllb-1 to lllb-36.
  • Such mixtures are preferably ternary mixture comprising one compound of formula I, which is selected from the compounds 1-1 to 1-18, as component 1 ), and one biopesticide II, which is selected from the biopesticides 11-1 to 11-14, in particular from the biopesticide strains lla-1 to lla- 1 1 , and one further active compound III, which may be selected from the insecticides llla-1 to llla-23, or the fungicides lllb-1 to lllb-36.
  • Pesticidal mixtures which comprise compound 1-1 , and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound I-2, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound I-3, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound I-4, and in which combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound I-5, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound I-6, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound I-7, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound I-8, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound I-9, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound 1-10, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound 1-12, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound 1-13, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound 1-14, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound 1-15, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound 1-16, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound 1-17, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • Pesticidal mixtures which comprise compound 1-18, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
  • the present invention relates to agriculatural compositions comprising a mixture of the invention, in particular any one of the mixtures A-1 to A-252 or B-1 to B-198, or I-1 -M-1 to I-1-M-1464, I-2-M-1 to I-2-M-1464, I-3-M-1 to I-3-M-1464, I-4-M-1 to I-4-M-1464, I-5- M-1 to I-5-M-1464, I-6-M-1 to I-6-M-1464, I-7-M-1 to I-7-M-1464, I-8-M-1 to I-8-M-1464, I-9-M-1 to I-9-M-1464, I-10-M-1 to I-10-M-1464, I-1 1-M-1 to 1-1 1 -M-1464, I-12-M-1 to I-12-M-1464, 1-13- M-1 to I-13-M-1464, I-14-M-1 to I-14-M-1464, I-15-M-1 to I-15-M-1464, I-16-M-1
  • composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • a predosage device usually from a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1 ) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
  • the present invention relates to a seed treatment composition
  • a seed treatment composition comprising an auxiliary and a mixture of the invention, preferably any one of the mixtures A-1 to A-252 or B-1 to B-198, or I-1 -M-1 to I-1-M-1464, I-2-M-1 to I-2-M-1464, I-3-M-1 to I-3-M-1464, I- 4-M-1 to I-4-M-1464, I-5-M-1 to I-5-M-1464, I-6-M-1 to I-6-M-1464, I-7-M-1 to I-7-M-1464, I-8-M- 1 to I-8-M-1464, I-9-M-1 to I-9-M-1464, I-10-M-1 to I-10-M-1464, I-1 1-M-1 to 1-1 1-M-1464, 1-12- M-1 to I-12-M-1464, I-13-M-1 to I-13-M-1464, I-14-M-1 to I-14-M-1464, I-15-M-1 to I-15-M-1464, I-16-
  • the seed treatment composition is in the form of a flowable concentrate FS, a solution LS, a powder for dry treatment DS, a water dispersible powder for slurry treatment WS, a water-soluble powder SS, an emulsion ES or EC, or a gel formulation, and is preferably in the form of a flowable concentrate.
  • the present invention relates to the use of a mixture of the invention, in particular a mixture selected from the mixtures A-1 to A-252 or B-1 to B-198, or 1-1 -M-1 to 1-1 -M- 1464, I-2-M-1 to I-2-M-1464, I-3-M-1 to I-3-M-1464, I-4-M-1 to I-4-M-1464, I-5-M-1 to I-5-M- 1464, I-6-M-1 to I-6-M-1464, I-7-M-1 to I-7-M-1464, I-8-M-1 to I-8-M-1464, I-9-M-1 to I-9-M- 1464, I-10-M-1 to I-10-M-1464, I-1 1-M-1 to 1-1 1 -M-1464, I-12-M-1 to I-12-M-1464, I-13-M-1 to I- 13-M-1464, I-14-M-1 to I-14-M-1464, I-15-M-1 to I-15-M-1464, I-16-M-1 to I
  • the present invention relates to a method for controlling invertebrate pests, which method comprises contacting the plant or the plant propagation material or the soil; the pests or their food supply, habitat or breeding grounds, with a pesticidally effective amount of a mixture of the invention, in particular a mixture selected from the mixtures A-1 to A-108 or B-1 to B-108, or a seed treatment composition as defined above.
  • the present invention relates to seeds comprising the mixture of the invention, in particular a mixture selected from the mixtures A-1 to A-252 or B-1 to B-198, or 1-1- M-1 to I-1-M-1464, I-2-M-1 to I-2-M-1464, I-3-M-1 to I-3-M-1464, I-4-M-1 to I-4-M-1464, I-5-M-1 to I-5-M-1464, I-6-M-1 to I-6-M-1464, I-7-M-1 to I-7-M-1464, I-8-M-1 to I-8-M-1464, I-9-M-1 to I- 9-M-1464, I-10-M-1 to I-10-M-1464, I-1 1 -M-1 to 1-1 1 -M-1464, I-12-M-1 to I-12-M-1464, I-13-M-1 to I-13-M-1464, I-14-M-1 to I-14-M-1464, I-15-M-1 to I-15-
  • the amount per 100 kg seeds is based on the weight of the pesticidal mixture irrespective of whether it is referred to the mixture as such or the seed treatment composition thereof.
  • Preferred seeds are seeds selected from wheat, maize, barley, oat, rye, rice, soybean, cotton, sugarbeet, rapeseed, and potato. With regard to all the mixtures of the invention as defined herein, the following embodiments are additionally preferred.
  • the mixtures of the present invention may be combined and applied in agriculture in mixture with other active ingredients, for example with other pesticides, insecticides, nematicides, fungicides, herbicides, safeners, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators.
  • active ingredients for example with other pesticides, insecticides, nematicides, fungicides, herbicides, safeners, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one mixture of the present invention.
  • An agrochemical composition comprises a pesticidally effective amount of a mixture of the present invention.
  • the term "pesticidally effective amount” is defined below.
  • compositions of the present invention 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. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Mono-graph No. 2, 6th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • 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, tackifi- ers and binders.
  • 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, tackifi- ers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo ⁇ hexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalene, alkyl
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch;
  • fertilizers e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas
  • products of vegetable origin e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth- oxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • Exam- pies of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are homo- or copolymers of
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the mixtures of the present invention on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Abstract

The present invention relates to pesticidal mixtures comprising as active components at least one active compound of formula (I) wherein the variables are as defined ni the specification, and at least one biopesticide II as defined in the specificartion. Furthermore, the present invention relates to seed treatment compositions comprising said mixtures, to methods and uses comprising the application of these mixtures and to seeds comprising the mixtures of the invention or a seed treatment composition thereof.

Description

Pesticidal mixture comprising a pyrazole compound and a biopesticide
Description The present invention relates to mixtures of active compounds having synergistically enhanced action and to methods and uses comprising applying said mixtures.
One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control.
Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests.
There also exists the need for pest control agents that combine knock-down activity with prolonged control, that is, fast action with long lasting action.
Another difficulty in relation to the use of pesticides is that the repeated and exclusive application of an individual pesticidal compound leads in many cases to a rapid selection of pests 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 induced by pesticides.
Furthermore, there is a desire for pesticide compounds or combinations of compounds, which when applied improve plants, which may result in "plant health", "vitality of plant propagation material" or "increased plant yield".
It is therefore an object of the present invention to provide pesticidal mixtures, which solve one or more than one of the discussed problems suche as
- reducing the dosage rate,
- enhancing the spectrum of activity,
- combining knock-down activity with prolonged control,
- improving resistance management,
- improving plant health,
- improving vitality of plant propagation material, also termed seed vitality,
- increasing plant yield.
It has been found that this object is in part or in whole achieved by the combination of active compounds defined below. The present invention relates to pesticidal mixtures comprising as active components
1 ) at least one active compound of formula I:
Figure imgf000002_0001
wherein
R1 is H, Ci-C2-alkyl, or Ci-C2-alkoxy-Ci-C2-alkyl;
R2 is CH3, or halomethyl; R3 is CN, d-Ce-alkyl, Ci-C6-haloalkyl, Ci-C2-alkoxy-Ci-C2-alkyl, C2-C6-alkenyl and C2-C6- alkynyl, C3-C6-cycloalkyl, Cs-Ce-cycloalkenyl, Ci-C6-alkoxy, wherein the C-atoms are unsubstituted, or partially or fully substituted by Ra,
Ra is halogen, CN, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C4-alkoxy, Ci-C2-haloalkoxy;
R4 is Ci-C4-alkyl, or a group mentioned for R3; or
R3 and R4 may together form Cs-Ce-cycloalkyl, which is unsubstituted, or partially or fully substituted by Ra;
R5 is H, or a group mentioned for R4;
and the stereoisomers, salts, tautomers and N-oxides thereof;
and
2) at least one biopesticide II selected from the groups L1 to L5:
L1 ) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila,
C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, C/onostachys rosea catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor a/bus, Paenibacillus alvei, Paenibacillus polymyxa, Pantoea vagans, Penicillium bilaiae, P.steckii, Phlebiopsis gig an tea, Pseudomonas sp., Pseudomonas ch/oraphis, Pseudozyma flocculosa, Pichia a noma la, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T.
asperellum, T. atroviride, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T.
stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii,
Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense
activator activity: harpin protein, Reynoutria sachalinensis extract;
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity:
Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp.
tenebrionis, Beauveria bass/ana, B. brongniartii, Burkho/deria sp., Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobacterium sp., Helicoverpa armigera nucleopolyhedrovirus (HearNPV),
Helicoverpa zea nucleopolyhedrovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopliae, Metarhizium anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteur/a sp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, S. feltiae, S.
kraussei, Streptomyces gal bus, S. micro flavus;
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1 -yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,1 1 ,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1-butanol, methyl eugenol, methyl jasmonate, jasmonic acid or salts or derivatives thereof, (E,Z)- 2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadien-1-ol acetate, (E,Z)-3,13-octadecadien-
1-ol, R-1-octen-3-ol, pentatermanone, (E,Z,Z)-3,8,1 1 -tetradecatrienyl acetate,
(Z,E)-9,12-tetradecadien-1-yl acetate, Z-7-tetradecen-2-one, Z-9-tetradecen-1-yl acetate, Z-1 1-tetradecenal, Z-1 1-tetradecen-1-ol, extract of Chenopodium ambrosiodes, Neem oil, Quillay extract;
L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth
promoting and/or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium sp., Rhizobium leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti;
in synergistically effective amounts.
Moreover, it has been found that simultaneous, that is joint or separate, application of one or more active compound(s) I and one or more biopesticide(s) II or successive application (that is immediately one after another and thereby creating the mixture "in-situ" on the desired location, as e.g. the plant) of one or more active compound(s) I and one or more biopesticide(s) II allows enhanced control of pests compared to the control rates that are possible with the individual compounds. Therefore, the term "mixture" as used herein is intended to include also
combinations.
The present invention also relates to a seed treatment composition comprising an auxiliary and a mixture of at least one active compound I and at least one biopesticide II as defined above.
The present invention also relates to the use of the mixture of at least one active compound I and at least one biopesticide II for protecting a plant, plant propagation material, or soil or water, in which the plants are growing, against the attack or infestation by invertebrate pests.
In particular, the present invention relates to the use of the mixture of at least one active compound I and at least one biopesticide II for protecting plant propagation material, preferably seeds, from soil insects and the seedlings' roots and shoots from soil and foliar insects, wherein the plant progagation material as e.g. the seeds are contacted with a pesticidally effective amount of the mixture before sowing and/or after pregermination.
The present invention further relates to a method for controlling invertebrate pests, which method comprises contacting the plant or the plant propagation material or the soil; the pests or their food supply, habitat or breeding grounds, with a pesticidally effective amount of the mixture of at least one active compound I and at least one biopesticide II.
The invention also provides seeds comprising the mixture of at least one active compound I and at least one biopesticide II.
The mixture(s) of at least one active compound of formula I with at least one biopesticide II are herein referred to as "mixture(s) according to the invention" or "mixture(s) of the invention", wherein the compounds of formula I are understood to include their stereoisomers, salts, tautomers or N-oxides, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof.
In a specific embodiment, the mixture according to the invention is a mixture of one active compound of formula I with one biopesticide II (binary mixture).
In another embodiment, the mixture according to the invention is a mixture of one active compound of formula I with at least one biopesticide II.
The term "composition(s) according to the invention" or "composition(s) of the present invention" encompasses composition(s) comprising the mixtures of the invention, i.e. mixtures of the compounds of formula I with at least one biopesticide II for being used and/or applied in methods according to the invention as defined herein, wherein the compounds of formula I are understood to include their stereoisomers, salts, tautomers or N-oxides, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N- oxide thereof.
Compounds of formula I are known from WO 2010/034738, WO 2012/084670,
WO 2012/143317, and US 61/891437 and can be prepared by the methods described therein. These compounds are known to be useful for combating invertebrate pests.
WO2012/084670 and WO 2013/189801 describe pesticidal mixtures of compounds of formula I with fungicides or insecticides. However, mixtures of compounds of formula I with
biopesticides have not been described previously.
The term "compound(s) of formula I" or "compound(s) according to the invention" comprises the compound(s) as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof. The term "compound(s) of the present invention" is to be understood as equivalent to the term "compound(s) according to the invention", therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof.
Depending on the substitution pattern, the compounds of the present invention may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention encompasses both the pure enantiomers or pure diastereomers of the compounds of the present invention, and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compounds of the present invention or their mixtures. Suitable compounds of the formula of the present invention also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof.
Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond, nitrogen-sulfur double bond or amide group.
The term "stereoisomer(s)" 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 compounds of the present invention may be present in the form of their N-oxides. The term "N-oxide" includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety. N-oxides of compounds of the present invention can in particular be prepared by oxidizing the ring nitrogen atom(s) of the pyridazine ring and/or the pyrazole ring with a suitable oxidizing agent, such as peroxo carboxylic acids or other peroxides. The person skilled in the art knows if and in which positions compounds of the present invention, i.e. of the formula I, may form N-oxides.
Salts of the compounds of the present invention are preferably agriculturally acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid if the compound of the present invention has a basic functionality or by reacting the compound with a suitable base if the compound of the present invention has an acidic functionality. In general, suitable "agriculturally useful salts" or "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 present 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 (NhV) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci- C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-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 Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
Preferred compounds of the present invention are compounds of formula I or a stereoisomer, N-oxide or salt thereof, wherein the salt is an agriculturally acceptable salt.
The compounds of of the formula I may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities. The present 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. Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, microbial and biochemical pesticides:
(1 ) Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classified as microbial pesticides, even though they are multi-cellular.
(2) Biochemical pesticides are naturally occurring substances or or structurally-similar and functionally identical to a naturally-occurring substance and extracts from biological sources that control pests or provide other crop protection uses as defined below, but have non-toxic mode of actions (such as growth or developmental regulation, attractents, repellents or defence activators (e.g. induced resistance) and are relatively non-toxic to mammals.
The biopesticides from group L1 ) and/or L2) may also have insecticidal, acaricidal, molluscidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L5) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
Many of these biopesticides have been deposited under deposition numbers mentioned herein (the prefices such as ATCC or DSM refer to the acronym of the respective culture collection, for details see e. g. here: http://www. wfcc.info/ccinfo/collection/by_acronym/), are referred to in literature, registered and/or are commercially available: mixtures of Aureobasidium pullulans DSM 14940 and DSM 14941 isolated in 1989 in Konstanz, Germany (e. g. blastospores in Blossom Protect® from bio-ferm GmbH, Austria), Bacillus amyloliquefaciens strain AP-188 (NRRL B-50615 and B-50331 ; US 8,445,255); B. amyloliquefaciens spp. plantarum D747 isolated from air in Kikugawa-shi, Japan (US 20130236522 A1 ; FERM BP-8234; e. g. Double Nickel™ 55 WDG from Certis LLC, USA), B. amyloliquefaciens spp. plantarum FZB24 isolated from soil in Brandenburg, Germany (also called SB3615; DSM 96-2; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. Taegro® from Novozyme Biologicals, Inc., USA), B. amyloliquefaciens ssp. plantarum FZB42 isolated from soil in Brandenburg, Germany (DSM 231 17; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. RhizoVital® 42 from AbiTEP GmbH, Germany), B.
amyloliquefaciens ssp. plantarum 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® from BASF Corp., USA), B. amyloliquefaciens ^.
plantarum QST-713 isolated from peach orchard in 1995 in California, U.S.A. (NRRL B-21661 ; e. g. Serenade® MAX from Bayer Crop Science LP, USA), B. amyloliquefaciens spp. plantarum TJ1000 isolated in 1992 in South Dakoda, U.S.A. (also called 1 BE; ATCC BAA-390; CA
2471555 A1 ; e. g. QuickRoots™ from TJ Technologies, Watertown, SD, USA), B. firm us CNCM 1-1582, a variant of parental strain EIP-N1 (CNCM 1-1556) isolated from soil of central plain area of Israel (WO 2009/126473, US 6,406,690; e. g. Votivo® from Bayer CropScience LP, USA), B. pumilus GHA 180 isolated from apple tree rhizosphere in Mexico (IDAC 260707-01 ; e. g. PRO- MIX® BX from Premier Horticulture, Quebec, Canada), B. pumilus INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tracheiphila (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumilus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL
B-30087; e. g. Sonata® or Ballad® Plus from Bayer Crop Science LP, USA), B. simplex ABU 288 (NRRL B-50304; US 8,445,255), B. subtilis FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA-1 1857; System. Appl. Microbiol. 27, 372-379, 2004; US 2010/0260735; WO 201 1/109395); B. thuringiensis ssp. aizawa/ABTS^ 857 isolated from soil taken from a lawn in Ephraim, Wisconsin, U.S.A., in 1987 (also called ABG-6346; ATCC SD-1372; e. g. XenTari® from BioFa AG, Munsingen, Germany), B. t. ssp. kurstaki ABTS-351 identical to HD-1 isolated in 1967 from diseased Pink Bollworm black larvae in Brownsville, Texas, U.S.A. (ATCC SD-1275; e. g. Dipel® DF from Valent Biosciences, IL, USA), B. t. ssp. tenebrionis NB-176-1 , a mutant of strain NB-125, a wild type strain isolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM 5480; EP 585 215 B1 ; e. g.
Novodor® from Valent Biosciences, Switzerland), Beauveria bassiana GHA (ATCC 74250; e. g. BotaniGard® 22WGP from Laverlam Int. Corp., USA), B. bassiana SWA (ATCC 74040; e. g. Naturalis® from CBC (Europe) S.r.l., Italy), Burkholderia sp. A396 isolated from soil in Nikko, Japan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc., USA), Coniothyrium m/n/tans COWMW -08 isolated from oilseed rape (WO 1996/021358; DSM 9660; e. g. Contans® WG, Intercept® WG from Bayer CropScience AG, Germany), harpin (alpha- beta) protein (Science 257, 85-88, 1992; e. g. Messenger™ or HARP-N-Tek from Plant Health Care pic, U.K.), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol. 107, 1 12-126, 201 1 ; e. g. Helicovex® from Adermatt Biocontrol, Switzerland; Diplomata® from Koppert, Brazil; Vivus® Max from AgBiTech Pty Ltd., Queensland, Australia), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (e. g. Gemstar® from Certis LLC, USA),
Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditis bacteriophora (e. g. Nemasys® G from BASF
Agricultural Specialities Limited, UK), Isaria fumosorosea Apopka-97 isolated from mealy bug on gynura in Apopka, Florida, U.S.A. (ATCC 20874; Biocontrol Science Technol. 22(7), 747- 761 , 2012; e. g. PFR-97™ or PreFeRal® from Certis LLC, USA), Metarhizium anisopliae var. anisopliae F52 also called 275 or V275 isolated from codling moth in Austria (DSM 3884, ATCC 90448; e. g. Met52® Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicola 277 isolated from grapes in the central part of Israel (US 6,994,849; NRRL Y-30752; e. g.
formerly Shemer® from Agrogreen, Israel), Paecilomyces ilacinus 251 isolated from infected nematode eggs in the Philippines (AGAL 89/030550; W01991/02051 ; Crop Protection 27, 352- 361 , 2008; e. g. BioAct®from Bayer CropScience AG, Germany and MeloCon® from Certis, USA), 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, 201 1 ; e.g. Clariva™ PN from Syngenta Crop Protection, LLC, USA), Penicillium bilaiae (also called P. bilaii) strains ATCC 18309 (= ATCC 74319), ATCC 20851 and/or ATCC 22348 (= ATCC 74318) originally isolated from soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can. J. Plant Sci. 78(1 ), 91-102, 1998; US 5,026,417, WO 1995/017806; e. g. Jump Start®, Provide® from Novozymes Biologicals BioAg Group, Canada), Reynoutria sachalinensis extract (EP 0307510 B1 ; e. g. Regalia® SC from Marrone Biolnnovations, Davis, CA, USA or Milsana® from BioFa AG, Germany), Steinernema carpocapsae (e. g. Millenium® from BASF Agricultural Specialities Limited, UK), S. feltiae {e. g. Nemashield® from BioWorks, Inc., USA; Nemasys® from BASF Agricultural Specialities Limited, UK), Streptomyces microflavus L B-50550
(WO 2014/124369; Bayer CropScience, Germany), T. harzianum -22 also called KRL-AG2 (ATCC 20847; BioControl 57, 687-696, 2012; e. g. Plantshield® from BioWorks Inc., USA or SabrEx™ from Advanced Biological Marketing Inc., Van Wert, OH, USA).
Preferred biopesticides, which have been deposited under deposition numbers mentioned herein (the prefices such as ATCC or DSM refer to the acronym of the respective culture collection, for details see e. g. here: http://www. wfcc.info/ccinfo/collection/by_acronym/), are referred to in literature, registered and/or are commercially available: mixtures of Aureobasidium pu/lu/ans DSM 14940 and DSM 14941 isolated in 1989 in Konstanz, Germany (e. g.
blastospores in Blossom Protect® from bio-ferm GmbH, Austria), Bacillus amyloliquefaciens strain AP-188 (NRRL B-50615 and B-50331 ; US 8,445,255); B. amyloliquefaciens spp.
plantarum D747 isolated from air in Kikugawa-shi, Japan (US 20130236522 A1 ; FERM
BP-8234; e. g. Double Nickel™ 55 WDG from Certis LLC, USA), B. amyloliquefaciens spp. plantarum FZB24 isolated from soil in Brandenburg, Germany (also called SB3615; DSM 96-2; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. Taegro® from Novozyme Biologicals, Inc., USA), B. amyloliquefaciens ssp. plantarum FZB42 isolated from soil in Brandenburg, Germany (DSM 231 17; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. RhizoVital® 42 from AbiTEP GmbH, Germany), B. amyloliquefaciens ssp. plantarum 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® from BASF Corp., USA), B. amyloliquefaciens pp.
plantarum QST-713 isolated from peach orchard in 1995 in California, U.S.A. (NRRL B-21661 ; e. g. Serenade® MAX from Bayer Crop Science LP, USA), B. amyloliquefaciens spp. plantarum TJ1000 isolated in 1992 in South Dakoda, U.S.A. (also called 1 BE; ATCC BAA-390; CA
2471555 A1 ; e. g. QuickRoots™ from TJ Technologies, Watertown, SD, USA), B. firm us CNCM 1-1582, a variant of parental strain EIP-N1 (CNCM 1-1556) isolated from soil of central plain area of Israel (WO 2009/126473, US 6,406,690; e. g. Votivo® from Bayer CropScience LP, USA), B. pumilus GHA 180 isolated from apple tree rhizosphere in Mexico (IDAC 260707-01 ; e. g. PRO- MIX® BX from Premier Horticulture, Quebec, Canada), B. pumilus INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tracheiphila (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumilus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL
B-30087; e. g. Sonata® or Ballad® Plus from Bayer Crop Science LP, USA), B. simplex ABU 288 (NRRL B-50304; US 8,445,255), B. subtilis FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA-1 1857; System. Appl. Microbiol. 27, 372-379, 2004; US 2010/0260735; WO 201 1/109395); B. thuringiensis ssp. aizawai NERSA %57 isolated from soil taken from a lawn in Ephraim, Wisconsin, U.S.A., in 1987 (also called ABG-6346; ATCC SD-1372; e. g. XenTari® from BioFa AG, Munsingen, Germany), B. t. ssp. kurstaki ABTS-351 identical to HD-1 isolated in 1967 from diseased Pink Bollworm black larvae in Brownsville, Texas, U.S.A. (ATCC SD-1275; e. g. Dipel® DF from Valent Biosciences, IL, USA), B. t. ssp. tenebrionis NB-176-1 , a mutant of strain NB-125, a wild type strain isolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM 5480; EP 585 215 B1 ; e. g.
Novodor® from Valent Biosciences, Switzerland), Beauveria bass/ana GHA (ATCC 74250; e. g. BotaniGard® 22WGP from Laverlam Int. Corp., USA), B. bassiana JW-λ (ATCC 74040; e. g. Naturalis® from CBC (Europe) S.r.l., Italy), Burkholderia sp. A396 isolated from soil in Nikko, Japan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc., USA), Coniothyrium m/n/tans COWMW -08 isolated from oilseed rape (WO 1996/021358; DSM 9660; e. g. Contans® WG, Intercept® WG from Bayer CropScience AG, Germany), harpin (alpha- beta) protein (Science 257, 85-88, 1992; e. g. Messenger™ or HARP-N-Tek from Plant Health Care pic, U.K.), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol. 107, 1 12-126, 201 1 ; e. g. Helicovex® from Adermatt Biocontrol, Switzerland; Diplomata® from Koppert, Brazil; Vivus® Max from AgBiTech Pty Ltd., Queensland, Australia), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (e. g. Gemstar® from Certis LLC, USA),
Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditis bacteriophora (e. g. Nemasys® G from BASF
Agricultural Specialities Limited, UK), Isaria fumosorosea Apopka-97 isolated from mealy bug on gynura in Apopka, Florida, U.S.A. (ATCC 20874; Biocontrol Science Technol. 22(7), 747- 761 , 2012; e. g. PFR-97™ or PreFeRal® from Certis LLC, USA), Metarhizium anisopliae ' var. anisopliae F52 also called 275 or V275 isolated from codling moth in Austria (DSM 3884, ATCC 90448; e. g. Met52® Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicola 277 isolated from grapes in the central part of Israel (US 6,994,849; NRRL Y-30752; e. g.
formerly Shemer® from Agrogreen, Israel), Paecilomyces ilacinus 2 \ isolated from infected nematode eggs in the Philippines (AGAL 89/030550; W01991/02051 ; Crop Protection 27, 352- 361 , 2008; e. g. BioAct®from Bayer CropScience AG, Germany and MeloCon® from Certis, USA), Pasteur/a 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, 201 1 ; e.g. Clariva™ PN from Syngenta Crop Protection, LLC, USA), Penicillium bilaiae (also called P. bilaii) strains ATCC 18309 (= ATCC 74319), ATCC 20851 and/or ATCC 22348 (= ATCC 74318) originally isolated from soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can. J. Plant Sci. 78(1 ), 91 -102, 1998; US 5,026,417, WO 1995/017806; e. g. Jump Start®, Provide® from Novozymes Biologicals BioAg Group, Canada), Reynoutria sachalinensis extract (EP 0307510 B1 ; e. g. Regalia® SC from Marrone Biolnnovations, Davis, CA, USA or Milsana® from BioFa AG, Germany), Steinernema carpocapsae (e. g. Millenium® from BASF Agricultural Specialities Limited, UK), S. feltiae {e. g. Nemashield® from BioWorks, Inc., USA; Nemasys® from BASF Agricultural Specialities Limited, UK), Streptomyces microflavus L B-50550
(WO 2014/124369; Bayer CropScience, Germany), T. harzianum -22 also called KRL-AG2 (ATCC 20847; BioControl 57, 687-696, 2012; e. g. Plantshield® from BioWorks Inc., USA or SabrEx™ from Advanced Biological Marketing Inc., Van Wert, OH, USA).
Preferred biopesticides on strain level are selected from the following groups L1 ) to L5):
L1 ) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Aureobasidium pullulans DSM 14940 and DSM 14941 (L1.1 ), Bacillus amy/o- liquefaciens AP-188 (L.1.2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B. amylo- liquefaciens ssp. plantarum FZB24 (L.1.4), B. amyloliquefaciens ssp. plantarum FZB42 (L.1.5), B. amyloliquefaciens ssp. plantarum MBI600 (L.1 .6), B. amyloliquefaciens ssp. plantarum QST-7 '13 (L.1.7), B. amyloliquefaciens ssp. plantarum ! ^ QQQ (L.1.8), B. pum/ius G 34 (L.1 .9), B. pum/ius GHA 180 (L.1.10), B. pumilus INR-7 (L.1.1 1 ), B.
pum/ius QSJ 2808 (L.1.13), B. simplex ABU 288 (L.1.14), B. subtilis FEM (L.1.15), Coniothyrium minitans CON/M/91-08 (L.1.16), Metschnikowia fructicola NRRL Y-30752 (L.1.17), Penicillium bilaiae ATCC 22348 (L.1.19), P. bilaiae ATCC 20851 (L.1.20), Penicillium bilaiae ATCC 18309 (L.1.21 ), Streptomyces microflavus NRRL B-50550 (L.1.22), T. harzianum T-22 (L.1.24);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense
activator activity: harpin protein (L.2.1 ), Reynoutria sachalinensis extract (L.2.2);
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity:
Bacillus firmus \-\ 82 (L.3.1 ); B. thuringiensis ssp. aizawai NSX§-\ 8 l (L.3.2), B. t. ssp. kurstaki ABTS-351 (L.3.3), B. t. ssp. tenebrionis NB-176-1 (L.3.5), Beauveria bassiana GHA (L.3.6), B. bassiana SWA (L.3.7), Burkholderia sp. A396 (L.3.9), Helicoverpa
nucleopolyhedrovirus (HearNPV) (L.3.10), Helicoverpa zea
nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.1 1 ), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (L.3.12), Heterohabditis bacteriophora (L.3.13), /ss /s fumosorosea Apopka-97 (L.3.14), Metarhizium anisop/iae ar. anisop/iae F52 (L.3.15), Paecilomyces Iilacinus 2 \ (L.3.16), Pasteuria nishizawae Pn (L.3.17), Steinernema carpocapsae (L.3.18), 5. /©///<=?e (L.3.19);
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or
nematicidal activity: cis-jasmone (L.4.1 ), methyl jasmonate (L.4.2), Quillay extract
(L.4.3);
in particular from
L1 ) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Aureobasidium pullulans DSM 14940 and DSM 14941 (L1.1 ), Bacillus amyloliquefaciens AP-188 (L.1 .2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B. amyloliquefaciens ssp. plantarum FZB24 (L.1.4), B. amyloliquefaciens ssp. plantarum FZB42 (L.1 .5), z5. amyloliquefaciens ssp. plantarum MBI600 (L.1.6), z5. amyloliquefaciens ssp. plantarum QST-713 (L.1.7), z5. amyloliquefaciens ssp. plantarum TJ1000 (L.1.8), /?. /¾y/77/7iys GB34 (L.1 .9), /?. /¾y/77/7iys GHA 180 (L.1 .10), B. pumilus INR-7 (L.1.1 1 ), B. pumilus QST 2808 (L.1.13), B. simplex ABU 288 (L.1.14), /?. si//W/s FB17
(L.1.15), Coniothyrium minitans CON/M/91 -08 (L.1.16), Metschnikowia fructicola NRRL Y-30752 (L.1.17), Penicillium bilaiae ATCC 22348 (L.1.19), P. bilaiae ATCC 20851 (L.1.20), Penicillium bilaiae ATCC 18309 (L.1.21 ), Streptomyces microti av us NRRL B- 50550 (L.1.22), ! harzianum -22 (L.1.24);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense
activator activity: harpin protein (L.2.1 ), Reynoutria sachalinensis extract (L.2.2);
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity:
Bac/i/us firmus \ A 582 (L.3.1 ); B. thuringiensis ssp. a/ ai/½3/'ABTS-1857 (L.3.2), z5. /. ssp. yre sA/ ABTS-351 (L.3.3), B. t. ssp. tenebrionis NB-176-1 (L.3.5), Beauveria bassiana GHA (L.3.6), /?. bassiana SWA (L.3.7), Burkholderia sp. A396 (L.3.9), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (L.3.10), Helicoverpa zea nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.1 1), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (L.3.12), Heterohabditis bacteriophora A S), Isaria fumosorosea Apopka- 97 (L.3.14), Metarhizium anisop/iae var. anisop/iae F52 (L.3.15), Paeci/omyces ///acinus 251 (L.3.16), Pasteur/a nishizawae Pn (L.3.17), Steinernema carpocapsae (L.3.18), 5.
/©/fee (L.3.19);
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or
nematicidal activity: cis-jasmone (L.4.1 ), methyl jasmonate (L.4.2), Quillay extract (L.4.3).
Preference is also given to mixtures comprising as pesticide II (component 2) a biopesticide selected from the groups L1 ), L3) and L5), preferably selected from strains denoted above as (L.1.2), (L.1.3), (L.1.4), (L.1 .5), (L.1 .6), (L.1 .7), (L.1.8), (L.1.10), (L.1 .1 1 ), (L.1.12), (L.1 .13), (L.1.14), (L.1.15), (L.1.17), (L.1 .18), (L.1.19), (L.1 .20), (L.1.21 ), (L.3.1 ); (L.3.9), (L.3.16), (L.3.17), (L.5.1 ), (L.5.2), (L.5.3), (L.5.4), (L.5.5), (L.5.6), (L.5.7), (L.5.8); (L.4.2), and (L.4.1 ); even more preferably selected from (L.1.2), (L.1.6), (L.1.7), (L.1.8), (L.1.1 1 ), (L.1 .12), (L.1.13), (L.1.14), (L.1.15), (L.1.18), (L.1 .19), (L.1.20), (L.1 .21 ), (L.3.1 ); (L.3.9), (L.3.16), (L.3.17), (L.5.1 ), (L.5.2), (L.5.5), (L.5.6), (L.4.2), and (L.4.1 ). Preference is also fiven to mixtures comprising as pesticide II (component 2) a biopesticide selected from strains (L.1.2), (L.1.3), (L.1.4), (L.1.5), (L.1.6), (L.1.7), (L.1.8), (L.1.10), (L.1 .1 1 ), (L.1.13), (L.1.14), (L.1.15), (L.1.17), (L.1 .19), (L.1.20), (L.1.21 ), (L.3.1 ); (L.3.9), (L.3.16), (L.3.17), (L.4.2), and (L.4.1 ); even more preferably selected from (L.1.2), (L.1.6), (L.1.7), (L.1.8), (L.1.1 1 ), (L.1.13), (L.1.14), (L.1.15), (L.1 .19), (L.1.20), (L.1.21 ), (L.3.1 ); (L.3.9), (L.3.16), (L.3.17), (L.4.2), and (L.4.1 ). These mixtures are particularly suitable for treatment of propagation mateials, i. e. seed treatment purposes and likewise for soil treatment. These seed treatment mixtures are particularly suitable for crops such as cereals, corn and leguminous plants such as soybean.
Preference is also given to mixtures comprising as pesticide II (component 2) a biopesticide selected from the groups L1 ), L3) and L5), preferably selected from strains denoted above as (L1.1 ), (L.1 .2), (L.1 .3), (L.1 .6), (L.1 .7), (L.1 .9), (L.1.1 1 ), (L.1.12), (L.1.13), (L.1.14), (L.1.15), (L.1.17), (L.1.18), (L.1.22), (L.1 .23), (L.1.24), (L.2.2); (L.3.2), (L.3.3), (L.3.4), (L.3.5), (L.3.6), (L.3.7), (L.3.8), (L.3.10), (L.3.1 1 ), (L.3.12), (L.3.13), (L.3.14), (L.3.15), (L.3.18), (L.3.19); (L.4.2), even more preferably selected from (L.1.2), (L.1.7), (L.1.1 1 ), (L.1 .13), (L.1.14), (L.1 .15), (L.1.18), (L.1.23), (L.3.3), (L.3.4), (L.3.6), (L.3.7), (L.3.8), (L.3.10), (L.3.1 1 ), (L.3.12), (L.3.15), and (L.4.2). Preference is also fiven to mixtures comprising as pesticide II (component 2) a biopesticide selected from strains (L1.1 ), (L.1.2), (L.1.3), (L.1.6), (L.1.7), (L.1 .9), (L.1 .1 1 ), (L.1.13), (L.1.14), (L.1.15), (L.1 .17), (L.1.22), (L.1 .24), (L.2.2); (L.3.2), (L.3.3), (L.3.5), (L.3.6), (L.3.7), (L.3.10), (L.3.1 1 ), (L.3.12), (L.3.13), (L.3.14), (L.3.15), (L.3.18), (L.3.19); (L.4.2), even more preferably selected from (L.1.2), (L.1.7), (L.1 .1 1 ), (L.1.13), (L.1.14), (L.1.15), (L.3.3), (L.3.6), (L.3.7), (L.3.10), (L.3.1 1 ), (L.3.12), (L.3.15), and (L.4.2).These mixtures are particularly suitable for foliar treatment. These mixtures for foliar treatment are particularly suitable for vegetables, fruits, vines, cereals, corn, leguminous crops such as soybeans.
For biopesticides II selected from groups L1 , L3, and L5, the mixtures of the invention embrace not only the isolated, pure cultures of the respective microorganisms as defined herein, but also its cell-free extract having pesticidal activity, preferably a ketone-based extract, its suspensions in a whole broth culture or as a metabolite-containing supernatant or a purified metabolite obtained from a whole broth culture of the microorganism or microorganism strain. "Whole broth culture" refers to a liquid culture containing both cells and media.
"Supernatant" or "culture medium" refers to the liquid broth remaining when cells grown in broth are removed by centrifugation, filtration, sedimentation, or other means well known in the art.
The term "metabolite" refers to any compound, substance or byproduct (including but not limited to small molecule secondary metabolites, polyketides, fatty acid synthase products, non- ribosomal peptides, ribosomal peptides, proteins and enzymes) produced by a microorganism (such as fungi and bacteria) that has pesticidal activity or improves plant growth, water use efficiency of the plant, plant health, plant appearance, or the population of beneficial microorganisms in the soil around the plant activity. The term "mutant" refers to a microorganism, obtained by direct mutant selection but also includes microorganisms that have been further mutagenized or otherwise manipulated (e. g., via the introduction of a plasmid). Accordingly, embodiments include mutants, variants, and or derivatives of the respective microorganism, both naturally occurring and artificially induced mutants. For example, mutants may be induced by subjecting the microorganism to known mutagens, such as N-methyl-nitrosoguanidine, using conventional methods. Preferably such mutants retain the pesticidal activity of the respective microorganism.
The remarks made below as to preferred embodiments of the variables (substituents) of the compounds of formula I are to be understood as preferred on their own as well as preferably in combination with each other, as well as in combination with the stereoisomers, tautomers, N- oxides or salts thereof, and in combination with the preferred embodiments of the biopesticides II of the pesticidal mixtures as defined herein, and, where applicable, as well as concerning the uses and methods according to the invention and the compositions according to the invention. The preferred embodiments of the variables of the compounds of formula I are defined hereinafter.
In one embodiment, R1 is H, CH3, C2H5, or CH2OCH3, preferably CH3, or C2H5.
In one embodiment, R2 is CH3.
In one embodiment, R3 is Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C6-cycloalkyl, wherein the C-atoms may be unsubstituted, or partially or fully substituted by halogen, or CN.
In a preferred embodiment, R3 is CH3, C2H5, CH(CH3)2, CH2CH2CH3, CF3, CHFCH3, cyclopropyl, wherein the ring is substituted by halogen, or CN.
In a further preferred embodiment, R3 is CH3, CH(CH3)2, CF3, CHFCH3, 1 -CN-c-C3H4.
In one embodiment, R4 is Ci-C4-alkyl, preferably CH3.
In another embodiment R3 and R4 together form Cs-Ce-cycloalkyl, wherein the C-atoms may be unsubstituted, or partially or fully substituted by halogen, or CN.
In one embodiment, R5 is H.
In another embodiment, R5 is H, and R4 is CH3.
In a further embodiment, R1 is CH3 or C2H5, R2 is CH3, R5 is H, and R4 is CH3, and R3 is selected from CH3, CH(CH3)2, CF3, CHFCH3, and 1 -CN-c-C3H4.
In one embodiment, the compound of formula I is a compound of formula IA as depicted below, wherein R2 is CH3 and
Figure imgf000013_0001
For the compounds of formula IA, it is particularly preferred that R1 is H, CH3, C2H5, or
Furthermore, it is preferred for the compounds of formula IA that R3 is CH3, C2H5, CH(CH3)2, CH2CH2CH3, CF3, CHFCH3, cyclopropyl, wherein the ring is substituted by halogen, or CN, and that R4 is Ci-C4-alkyl, or that R3 and R4 together form Cs-Ce-cycloalkyl, which is unsubstituted, or partially or fully substituted by halogen, or CN.
Particularly preferred compounds of formula I are compounds of formula IA, wherein the variables R1, R3, and R4 correspond to one row of table I below. Said compounds are referred to as compounds 1-1 to 1-18 in accordance with each row of table I.
Table I
Figure imgf000014_0001
Figure imgf000014_0002
With regard to the compounds I-2, I-3, I-4, I-5, I-8, I-9, 1-10, 1-1 1 , 1-14, 1-15, 1-16, 1-17, it is to be understood, as explained above, that the compounds may be present in two enantiomeric forms, which are all understood to be encompassed by the present invention, either in isolated form or as a mixture. In addition to the above defined compound of formula I, i.e. component 1 ), the pesticidal mixtures of the invention comprise a component 2), which is a biopesticide II, which is selected from the groups L1 to L5 as defined above. Preferred biopesticides II are defined hereinafter.
The preferred embodiments regarding biopesticides II, which may be selected as component 2) of the mixtures of the invention, are to be understood as preferred on their own as well as preferably in combination with the preferred embodiments of the compounds of formula I, i.e. component 1 ) of the mixture of the invention, and, where applicable, as well as concerning the uses and methods according to the invention and the compositions according to the invention.
Preference is given to mixtures comprising as biopesticide II (component 2) a biopesticide selected from group L1 , preferably selected from Bacillus amyloliquefaciens herein even more preferably from strains AP-136, AP-188, AP-218, AP-219, AP-295, IN937a, IT-45; B.
amyloliquefaciens ssp. plantarum (formerly called B. subtilis or B. subtilis spp.
amyloliquefaciens) herein even more preferably from strains MBI600, D747, FZB24, FZB42, GB03, QST-713 and TJ1000; B. mojavensis AP-209; B. pumilus herein even more preferably from strains GHA 180, INR-7, and QST 2808; B. simplex here'm more preferably strain ABU 288; B. so/isa/si herein more preferably strain AP-217; B. subtilis herein even more preferably selected from strains CX-9060, FB17 and GB07; Muscodor a/bus herein more preferably strains QST 20799 and SA-13; Paenibacillus polymyxa herein more preferably strain PKB1 ,
Penicillium bilaiae herein more preferably strains ATCC 22348, ATCC 20581 and ATCC 18309; Pseudomonas fluorescens herein more preferably strain A506; Sphaerodes mycoparasitica herein more preferably strain SMCD2220; ; Trichoderma harzianum herein more preferably strain T-22; Trichoderma virens herein more preferably strais GI-3 and G-41.
Preference is also given to mixtures comprising as biopesticide II (component 2) a biopesticide selected from group L1 , even more preferably selected from B. amyloliquefaciens AP-188, B. amylolique faciens ssp. plantarum MBI600, B. amyloliquefaciens ssp. plantarum QST -1 ?>, B. pumilus INR-7, /?. pumilus QST 2808, /?. simplex ABU 288, and /?. si//W/s FB17.
According to one embodiment of the inventive mixtures, the at least one biopesticide II is Bacillus amyloliquefaciens ssp. plantarum MBI600. These mixtures are particularly suitable in soybean.
According to another embodiment of the inventive mixtures, the at least one biopesticide II is B. pumilus INR-7. These mixtures are particularly suitable in soybean and corn.
According to a further embodiment, the at least one biopesticide II is Bacillus simplex, preferably B. simplex ABU 288. These mixtures are particularly suitable in soybean and corn.
According to a further embodiment, the at least one biopesticide II is Bacillus subtilis, preferably B. subtilis strain FB17.
According to one embodiment of the inventive mixtures, the at least one biopesticide II is selected from Bacillus amyloliquefaciens AP-136, B. amyloliquefaciens AP-188, B.
amyloliquefaciens AP-218, B. amyloliquefaciens AP-219, B. amyloliquefaciens AF '-295, B.
amyloliquefaciens spp. plantarum FZB24, B. amyloliquefaciens ssp. plantarum FZB42, B.
amyloliquefaciens ssp. plantarum Ί "J 1000, B. amyloliquefaciens ssp. plantarum D7 '47, B.
amyloliquefaciens ssp. plantarum MBI600, B. amyloliquefaciens spp. plantarum GB03, z5.
amyloliquefaciens spp. plantarum QST "-713, z5. mojavensis AP-209, z5. pumilus GB34, z5.
pumilus INR-7, z5. pumilus QST 2808, z5. pumilus GHA 180, z5. simplex ABU 288, z5. solisalsi AP-217, z5. subti/is CX-9060, B. subtilis FB17 and z5. s ubti/is GB07. These mixtures are particularly suitable in soybean and corn, in particular for seed treatment.
According to a further embodiment, the at least one pesticide II is selected from Streptomyces spp., preferably from 5. griseoviridis, S. lydicus and 5. violaceusniger, in particular from strains 5. griseoviridis Υ&Λ , S. iydicus \NYEC 108, 5. violaceusniger XL-2 and 5. vio/aceusnigerYCED- 9.
According to one embodiment of the inventive mixtures, the at least one biopesticide II is selected from the following fungi Coniothyrium minitans CON/M/91-08, 7! harzianum T-22, 7! i//re/7s GI-3, 7! wjre/7s GL-21 , 7! wjre/7s G-41. These mixtures are particularly suitable for seed and/or soil treatment.
According to a further embodiment, the at least one biopesticide II is selected from Pseudo- monas spp., preferably selected from P. chloraphis herein more preferably strain MA 342 and Pseudomonas sp. DSM 13134; P. fluorescens herein more preferably selected from strains A506, WCS 374 and Pf-5; and P. put/da herein more preferably strain ATCC 202153.
The present invention also relates to mixtures wherein the at least one biopesticide II is selected from the fungal genus Trichoderma, preferably from the strains T. asperellum T34, T. asperellum SKT-1 , T. asperellum ICC 012, T. asperellum ~V^\ , T. atroviride LC52, T. atroviride CNCM 1-1237, T. gamsii \CC 080, T. harmatum JH 382, T. harzianum -22, T. harzianum T-35, T. harzianum T-39, T. harzianum T-315; mixture of T. harzianum ICC012 and T. gamsii \CC080; mixture of T. polysporum and T. harzianum, T. stromaticum, T. virens GI-3, T. virens ^ GL-21 , T. virens Gi- Λ .
The present invention also relates to mixtures wherein the at least one biopesticide II is selected from the fungal species Muscodor a/bus preferably from the strains SA-13 and QST 20799, which are particularly suiable for soil and seed treatment against soil-borne pathogens and/or nematodes.
Preference is given to mixtures comprising as biopesticide II (component 2) a biopesticide selected from group L3), preferably selected from Bacillus firmus herein preferably strain 1-1582, Beauveria bass/ana herein preferably selected from strains GHA, H123, and DSM 12256;
Burkholderia sp. and herein preferably strain A396, Metarhizium anisopliae var. acr/dum herein preferably strain IMI 330189, M. anisopliae herein preferably selected from strains FI-985, Fl- 1045, F52 and ICIPE 69; Paecilomyces ///acinus herein preferably selected from strains 251 , DSM 15169 and BCP2, Paenibacillus popilliae herein preferably selected from strains
Dutky-1940, KLN 3 and Dutky 1 ; Pasteur/a nishazawa and herein preferably strain Pn1 .
Preference is also given to mixtures comprising as biopesticide II (component 2) a biopesticide selected from group L3), even more preferably from B. bass/ana DSM 12256, Metarhizium anisopliae var. acr/dum \M\ 330189, M. anisopliae FI-985, M. anisopliae FI-1045, Paecilomyces lilacinus DSM 15169, P. niacin us BCP2, P. lilacinus 251 , Paenibacillus popilliae Dutky-1940, P. popilliae KLN 3 and P. popilliae Dutky 1 .
According to a further embodiment, the at least one biopesticide II is Beauveria brongniartii. According to a further embodiment, the at least one biopesticide II is Metarhizium anisopliae or M. anisopliae var. acridium, preferably selected from M. anisopliae FI-1045, M. anisopliae F52, M. anisopliae var. acr/dum strains FI-985 and IMI 330189; in particular strain IMI 330189. These mixtures are particularly suitable for control of arthropod pests in soybean and corn.
According to a further embodiment, the at least one biopesticide II is Paecilomyces fumoso- roseus, preferably strain FE 9901 especially for white fly control.
According to a further embodiment, the at least one biopesticide II is selected from Nomuraea rileyi, preferably strains SA86101 , GU87401 , SR86151 , CG128 and VA9101 ; and P. lilacinus, preferably strains 251 , DSM 15169 or BCP2, in particular BCP2, which strains especially control the growth of plant-pathogenic nematodes.
According to a further embodiment, the at least one biopesticide II is Bacillus firmus, preferably spores of strain CNCM 1-1582, preferably useful for seed treatment of cereals, soybean, cotton, sugarbeets and corn against nematodes and insects.
According to a further embodiment, the at least one biopesticide II is Pasteur/a nishizawae, preferably spores of strain Pn1 , preferably useful for seed treatment of cereals, soybean, cotton, sugarbeets and corn against nematodes and insects.
According to a further embodiment, the at least one biopesticide II is Flavobacterium sp., preferably spores of strain H492, preferably useful for seed treatment of cereals, soybean, cotton, sugarbeets and corn against nematodes and insects.
According to a further embodiment, the at least one biopesticide II is Bacillus cereus, preferably spores of CNCM 1-1562, preferably useful for seed treatment of soybean, cotton, cereals, and corn against nematodes and insects.
According to a further embodiment, the at least one biopesticide II is Burkholderia sp., preferably strain A396, preferably useful for seed treatment of soybean, cotton, cereals, and corn.
According to a further embodiment, the at least one biopesticide II is Paecilomyces lilacinus 251 , preferably useful for seed treatment of soybean, cotton, cereals, and corn. According to a further embodiment, the at least one biopesticide II is a mixture of spores of B. firmus and B. cereus, preferably mixtures spores of above mentioned strains CNCM 1-1582 and CNCM 1-1562, preferably useful for seed treatment of soybean, cotton, cereals, and corn against nematodes and insects.
According to one preferred embodiment of the inventive mixtures, the at least one pesticide II is selected from Bacillus firmus CNCM 1-1582, Paecilomyces lilacinus 251 , Pasteuria nishizawa Pn1 and Burkholderia sp. A396 having nematicidal, acaricidal and/or insecticidal activity. These mixtures are particularly suitable in soybean, cotton, cereals, and corn, in particular for seed treatment.
Preference is also given to mixtures comprising as biopesticide II (component 2) a biopesticide selected from group L4), preferably methyl jasmonate.
Preference is also given to mixtures comprising as biopesticide II (component 2) a biopesticide selected from group L5), preferably selected from Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp. (Arachis), Bradyrhizobium sp.
(Vigna), B. elkanii, B. japonicum; Paenibacillus alvei, Penicillium bilaiae, Rhizoblum
leguminosarum bv. phaseo/i, R. I. bv. trifolii, R. I. bv. viciae, and Sinorhizobium meliloti.
Preference is also given to mixtures comprising as biopesticide II (component 2) a biopesticide selected from group L5) selected from Azospirillum amazonense SpY2, A. brasilense XOH, A. brasilense Cd, A. lipoferum Sp31 , Bradyrhizobium sp. (Vigna) PNL1 , B. japonicum TA-1 1 ,
Peniciillium bilaiae strains ATCC 18309, ATCC 20851 and ATCC 22348; Rhizobium
leguminosarum b . phaseoli RG-B10, R. I. bv. viciae P1 NP3Cst, R. I. bv. viciae RG-P2, R. I. bv. trifolii RP1 13-7, R. I. bv. viciae SU303, R. I. bv. viciae WSM1455, R. tropic/ SEMA 4077, R. tropic/ PRF 81 and Sinorhizobium meliloti, even more preferably selected from Bradyrhizobium sp. (Vigna) PNL1 , B. japonicum TA-1 1.
The present invention also relates to mixtures, wherein the at least one biopesticide II is selected from Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense and A.
halopraeferens, more preferably from A. brasilense. These are particularly suitable in soybean, especially as seed treatment.
In one embodiment, component 2), i.e. the biopesticide II, of the mixtures of the invention is selected from Azospirillum amazonense, Azospirillum brasilense, Azospirillum lipoferum, Azospirillum irakense, Azospirillum halopraeferens, Bradyrhizobium spp., Bradyrhizobium sp. (Arachis), Bradyrhizobium sp. (Vigna), Bradyrhizobium elkanii, Bradyrhizobium japonicum,
Bradyrhizobium liaoningense, Bradyrhizobium lupini, Dei ft/a ac/dovorans, Glomus intraradices, Mesorhizobium sp., Mesorhizobium ciceri, Mesorhizobium huakii, Mesorhizobium lot/,
Rhizobium leguminosarum bv. phaseoli, Rhizobium leguminosarum bv. trifolii, Rhizobium leguminosarum bv. viciae, Rhizobium tropic/', Sinorhizobium meliloti, Bacillus altitudinis, Bacillus amyloliquefaciens, Bacillus amyloliquefaciens ssp. plantarum, Bacillus firmus, Bacillus megaterium, Bacillus mojavensis, Bacillus mycoides, Bacillus pumilus, Bacillus simplex, Bacillus solisalsi, Bacillus subtilis, Burkholderia sp., Coniothyrium m in/ tans, Paecilomyces ///acinus, Paenibacillus alvei, Paenibacillus polymyxa, Paenibacillus popilliae, Pasteuria nishizawae, Pasteuria usgae, Penicillium bilaiae, Pseudomonas chloraphis, Pseudomonas fluorescens, Pseudomonas put/da, abscisic acid, harpin protein (alpha-beta), jasmonic acid or salts or derivatives thereof, cis-jasmone, methyl jasmonate.
In a preferred embodiment, component 2), i.e. the biopesticide II, of the mixtures of the invention is selected from Azospirillum amazonense SpY2, Azospirillum brasilense AZ39 also called Az 39, Azospirillum brasilense Cd, Azospirillum brasilense Sp 245, Azospirillum brasilense XOH, Azospirillum lipoferum Sp31 , Bradyrhizobium elkanii J- 30 , Bradyrhizobium elkanii U-1302, Bradyrhizobium elkanii \JSOfk 3254, Bradyrhizobium elkanii USDA 76,
Bradyrhizobium elkanii S DA 94, Bradyrhizobium japonicum G49, Bradyrhizobium japonicum SEMIA 566, Bradyrhizobium japonicum ! Ά-1 1 (TA1 1 NOD+), Bradyrhizobium japonicum USDA 1 10, Bradyrhizobium japonicum USDA 121 , Bradyrhizobium japonicum USDA 3,
Bradyrhizobium japonicum USDA 31 , Bradyrhizobium japonicum USDA 76, Bradyrhizobium sp. (Arachis) CB1015, Bradyrhizobium sp. (Arachis) SEMIA 6144, Bradyrhizobium sp. (Arachis) SEMIA 6462, Bradyrhizobium sp. (Arachis) SEMIA 6464, Bradyrhizobium sp. (Vigna) PNL1 , Mesorhizobium sp. WSM1497, Rhizobium leguminosarum by. phaseoli RG-B 0, Rhizobium leguminosarum by. trifolii Ό95, Rhizobium leguminosarum bv. trifolii CB782, Rhizobium leguminosarum by. trifolii 'CC1099, Rhizobium leguminosarum ' bv. trifolii CC275e, Rhizobium leguminosarum b . trifolii CC283b, Rhizobium leguminosarum b . trifolii 'RP1 13-7 ', Rhizobium leguminosarum b . trifolii! Ά1 , Rhizobium leguminosarum by. trifolii WSM1325, Rhizobium leguminosarum by. trifolii \NSM2304, Rhizobium leguminosarum bv . wc/ae P1 NP3Cst also referred to as 1435, Rhizobium leguminosarum bv. wc/ae RG-P2 also called P2, Rhizobium leguminosarum bv. wc/ae SU303, Rhizobium leguminosarum bv. i//c?/ae WSM1455, Rhizobium tropic/ 'CC51 1 , Rhizobium tropiciC\AJ 899, Rhizobium tropici W\2, Rhizobium tropici PRF 81 , Sinorhizobium /77e///o// NRG185, Sinorhizobium /77e///o// RCR201 1 also called 201 1 or SU47, Sinorhizobium meliloti, RRI 128, Bacillus altitudinis 41 KF2b, Bacillus amyloliquefaciens AP-136, Bacillus amyloliquefaciens AP-188, Bacillus amyloliquefaciens AP-218, Bacillus
amyloliquefaciens AP-219, Bacillus amyloliquefaciens AP-295, Bacillus amyloliquefaciens ssp. plantarum Ό7Α7, Bacillus amyloliquefaciens ssp. plantarum FZB24 also called SB3651 , Bacillus amyloliquefaciens ssp. plantarum FZB42, Bacillus amyloliquefaciens ssp. plantarum GB03 also called GB03 formerly z5. subtilis, Bacillus amyloliquefaciens ssp. plantarum MBI600 also referred to as 1430, formerly B. subtilis, Bacillus amyloliquefaciens ssp. plantarum QST-713, formerly B. subtilis, Bacillus amyloliquefaciens ssp. plantarum J1000, also called 1 BE, Bacillus firmus CNCM 1-1582, Bacillus megaterium H491 , Bacillus megaterium J 142, Bacillus megaterium M018, Bacillus mojavensis AP-209, Bacillus mojavensis SR1 1 , Bacillus mycoides AQ726, Bacillus mycoides J also called BmJ, Bacillus pumilus GB34, Bacillus pumilus GHA 180, Bacillus pumilus INR-7 otherwise referred to as BU F22 and BU-F33, Bacillus pumilus QST 2808, Bacillus simplex ABU 288, Bacillus subtilis CX-9060 , Bacillus subtilis FB17, Bacillus subtilis GB07, Burkholderia sp. A396, Coniothyrium minitans CON/M/91-08, Paecilomyces Iilacinus 2 \ , Paecilomyces ///acinus BCP2, Paen/bac/i/us polymyxa PKB1 , Paenibacillus popilliae 14F-D80 also called K14F-0080, Paenibacillus popilliae KLN 3, Pasteur/a nishizawae Pn1 , Pasteur/a sp. Ph3, Pasteur/a sp. Pr3, Pasteur/a sp. ATCC PTA-9643, Pasteur/a usage BL1 , Penic/i/ium b/ia/ae (also called . s//) NRRL 50162, Penic/i/ium b/ia/ae (also called . MM) NRRL 50169, Penic/i/ium b/ia/ae (also called P. MM) ATCC 18309 (= ATCC 74319), Penic/i/ium bilaiae (also called P. Ms//) ATCC 20851 , Penic/i/ium b/ia/ae (also called P. MM) ATCC 22348 (=ATCC 74318), Pseudomonas f/uorescens A506, Pseudomonas f/uorescens ATCC 13525, Pseudomonas fluorescens CH AO, Pseudomonas fluorescens CL 145A,
Pseudomonas fluorescens C\ 12089, Pseudomonas fluorescens Pf-5, Pseudomonas fluorescens WCS374, Pseudomonas putida ATCC 202153. In one embodiment, component 2), i.e. the biopesticide II, of the mixtures of the invention is selected from
L1 ) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila,
C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor a/bus, Paenibacillus alvei, Paenibacillus polymyxa, Pantoea vagans, Penicillium bilaiae, Psteck/i, Phlebiopsis gig an tea, Pseudomonas sp., Pseudomonas ch/oraphis, Pseudozyma flocculosa, Pichia a noma la, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T.
asperellum, T. atroviride, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T.
stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii,
Verticillium dahlia;
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense
activator activity: harpin protein, Reynoutria sachalinensis extract;
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity:
Agrobacterium radiobacter, Bacillus cereus, B. firmus, Burkholderia sp.,
Chromobacterium subtsugae, Flavobacterium sp., Paecilomyces fumosoroseus, P. niacin us, Paenibacillus popilliae, Pasteur/a sp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Streptomyces galbus, S. micro flavus, L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or
nematicidal activity: cis-jasmone, methyl jasmonate, jasmonic acid or salts or derivatives thereof;
L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth
promoting and/or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp., B. elkanii, B. japonicum,
B. liaoningense, B. lupini, Dei ft/a acidovorans, Glomus intraradices, Mesorhizobium sp., Rhizobium leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropic/, Sinorhizobium meliloti. In a preferred embodiment, component 2), i.e. the biopesticide II, of the mixtures of the invention is selected from the group L1 , i.e. microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B.
mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. eaten Ό '/ate (also named Gliocladium eaten ulatum), Gliocladium roseum, Lysobacter antibioticus, L enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus polymyxa, Pantoea vagans, Penicillium bilaiae, P. steckii, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas ch/oraphis, Pseudozyma flocculosa, Pichia a noma la, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T. asperellum, T. atroviride, T. gams/I, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia.
In a more preferred embodiment, component 2), i.e. the biopesticide I I, of the mixtures of the invention is selected from Bacillus amyloliquefaciens, Bacillus pumilus, Bacillus simplex, and Bacillus subtilis, in particular from the strains Bacillus amyloliquefaciens MBI600, B.
amyloliquefaciens AP-188, Bacillus pumilus INR-7 (otherwise referred to as BU-F22 and BU- F33), Bacillus simplex ABU 288, and Bacillus subtilis FB17 (also called UD 1022 or UD10-22). According to one particularly preferred embodiment, the biopesticide II of the mixtures of the invention is Bacillus pumilus, preferably spores of strain INR-7.
According to another particularly preferred embodiment, the biopesticide II of the mixtures of the invention is Bacillus simplex, preferably spores of strain ABU 288.
According to another particularly preferred embodiment, the biopesticide II of the mixtures of the invention is Bacillus subtilis, preferably spores of strain FB17.
In a further preferred embodiment, component 2), i.e. the biopesticide II, of the mixture of the invention is Penicillium steckii, preferably Penicillium steckii strain IBWF104-06 as deposited with DSMZ under the deposit number DSM 27859. Strain IBWF104-06 was determined to have potent antifungal activity, in particular, against infestion with plant pathogens including
Phytophthora infestans, Botrytis cinerea and Alternaria solani (PCT/EP2014/074165).
In another preferred embodiment, component 2), i.e. the biopesticide II, of the mixtures of the invention is selected from the group L2, i.e. biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract.
According to one particularly preferred embodiment, the biopesticide II of the mixture of the invention is harpin protein (alpha-beta). In another preferred embodiment, component 2), i.e. the biopesticide II, of the mixtures of the invention is selected from the group L4, i.e. biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: cis-jasmone, methyl jasmonate, jasmonic acid or salts or derivatives thereof.
According to one particularly preferred embodiment, the biopesticide II of the mixtures of the invention is cis-jasmone.
According to another particularly preferred embodiment, the biopesticide II of the mixture of the invention is methyl jasmonate.
According to another particularly preferred embodiment, the biopesticide II of the mixture of the invention is jasmonic acid or a salt or derivative thereof. In a particularly preferred embodiment, component 2), i.e. the biopesticide II, of the mixtures of the invention is selected from the group L3, i.e. microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, Burkholderia sp., Chromobacterium subtsugae, Flavobacterium sp., Paecilomyces
fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteur/a sp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Streptomyces galbus, S.
micro f/avus.
In a more preferred embodiment, component 2), i.e. the biopesticide I I, of the mixtures of the invention is selected from Bacillus firmus, Pasteur/a nishazawa sp., Flavobacterium sp., Paecilomyces lilacinus, and Burkholderia sp, in particular from the strains Burkholderia sp. A396, Paecilomyces lilacinus 251 , Bacillus firmus CNCM 1-1582, Pasteur/a nishizawae - Pn1 , and Flavobacterium sp. H492.
In an even more preferred embodiment, component 2), i.e. the biopesticide II, of the mixtures of the invention is selected from Bacillus firmus, Pasteur/a nishizawa, and Flavobacterium sp., in particular from the strains Bacillus firmus CNCM 1-1582, Pasteur/a nishizawae Pn1 , and Flavobacterium sp. H492.
According to one particularly preferred embodiment, the biopesticide II of the mixtures of the invention is Bacillus cereus, preferably spores of strain CNCM 1-1562.
According to another particularly preferred embodiment, the biopesticide II of the mixtures of the invention is Burkholderia sp., preferably strain A396.
According to another particularly preferred embodiment, the biopesticide II of the mixtures of the invention is Paecilomyces lilacinus, preferably strain 251 , DSM 15169 or BCP2, particularly preferably strain 251 .
According to another particularly preferred embodiment, the biopesticide II of the mixtures of the invention is Bacillus firmus, preferably spores of strain CNCM 1-1582; e.g. VOTiVO® from Bayer CropScience LP, USA, which is suitable for nematode control.
According to another particularly preferred embodiment, the biopesticide II of the mixtures of the invention is Pasteur/a nishizawae, preferably spores of strain Pn1 , e.g. Clariva® PN from Syngenta Crop Protection, LLC, USA, which is suitable for nematode control.
According to yet another particularly preferred embodiment, the biopesticide II of the mixtures of the invention is Flavobacterium sp., preferably spores of strain H492, e.g. MBI-302 from Marrone Bio Innovations, USA, which is suitable for nematode control. In summary, particularly preferred biopesticides II may be selected from the following biopesticides 11-1 to 11-14 in accordance with each row of table II, of which biopesticides 11-12, I ll s, and 11-14 are particularly preferred.
Table II
No biopesticide No biopesticide
11-1 Bacillus amyloliquefaciens II-5 Penicillium steckii
II-2 Bacillus pumilus II-6 harpin protein (alpha-beta)
II-3 Bacillus simplex II-7 cis-jasmone
II-4 Bacillus subtilis II-8 methyl jasmonate No biopesticide No biopesticide jasmonic acid or a salt or 11-12 Bacillus firmus
II-9
derivative thereof 11-13 Pasteur/a nishizawae
11-10 Burkholderia sp. 11-14 Flavobacterium sp.
11-1 1 Paecilomyces lilacinus
Furthermore, particularly preferred strains of biopesticides II may be selected from the following biopesticide strains lla-1 to lla-1 1 in accordance with each row of table I la, of which the biopesticide strains lla-9, lla-10, and lla-1 1 are particularly preferred.
Table Ma
Figure imgf000022_0002
Figure imgf000022_0001
In the context of the present invention, the following mixtures of compounds I and biopesticides II as in Table A are preferred and represent embodiments of the invention:
Table A
No. I II No. I II No. I II
A-1 1-1 11-1 A-20 I-2 II-2 A-39 I-3 II-3
A-2 I-2 11-1 A-21 I-3 II-2 A-40 I-4 II-3
A-3 I-3 11-1 A-22 I-4 II-2 A-41 I-5 II-3
A-4 I-4 11-1 A-23 I-5 II-2 A-42 I-6 II-3
A-5 I-5 11-1 A-24 I-6 II-2 A-43 I -7 II-3
A-6 I-6 11-1 A-25 I-7 II-2 A-44 I-8 II-3
A-7 I -7 11-1 A-26 I-8 II-2 A-45 I-9 II-3
A-8 I-8 11-1 A-27 I-9 II-2 A-46 1-10 II-3
A-9 I-9 11-1 A-28 1-10 II-2 A-47 1-1 1 II-3
A-10 1-10 11-1 A-29 1-1 1 II-2 A-48 1-12 II-3
A-1 1 1-1 1 11-1 A-30 1-12 II-2 A-49 1-13 II-3
A-12 1-12 11-1 A-31 1-13 II-2 A-50 1-14 II-3
A-13 1-13 11-1 A-32 1-14 II-2 A-51 1-15 II-3
A-14 1-14 11-1 A-33 1-15 II-2 A-52 1-16 II-3
A-15 1-15 11-1 A-34 1-16 II-2 A-53 1-17 II-3
A-16 1-16 11-1 A-35 1-17 II-2 A-54 1-18 II-3
A-17 1-17 11-1 A-36 1-18 II-2 A-55 1-1 II-4
A-18 1-18 11-1 A-37 1-1 II-3 A-56 I-2 II-4
A-19 1-1 II-2 A-38 I-2 II-3 A-57 I-3 II-4 No. I II No. I II No. I II
A-58 I-4 II-4 A-99 I-9 II-6 A-140 1-14 II-8
A-59 I-5 II-4 A- 100 1-10 II-6 A-141 1-15 II-8
A-60 I-6 II-4 A-101 1-11 II-6 A-142 1-16 II-8
A-61 I -7 II-4 A- 102 1-12 II-6 A-143 1-17 II-8
A-62 I-8 II-4 A- 103 1-13 II-6 A-144 1-18 II-8
A-63 I-9 II-4 A- 104 1-14 II-6 A-145 1-1 II-9
A-64 1-10 II-4 A- 105 1-15 II-6 A-146 I-2 II-9
A-65 1-11 II-4 A- 106 1-16 II-6 A-147 I-3 II-9
A-66 1-12 II-4 A- 107 1-17 II-6 A-148 I-4 II-9
A-67 1-13 II-4 A- 108 1-18 II-6 A-149 I-5 II-9
A-68 1-14 II-4 A- 109 1-1 II-7 A-150 I-6 II-9
A-69 1-15 II-4 A-110 I-2 II-7 A-151 I -7 II-9
A-70 1-16 II-4 A-111 I-3 II-7 A-152 I-8 II-9
A-71 1-17 II-4 A-112 I-4 II-7 A-153 I-9 II-9
A-72 1-18 II-4 A-113 I-5 II-7 A-154 1-10 II-9
A-73 1-1 II-5 A-114 I-6 II-7 A-155 1-11 II-9
A-74 I-2 II-5 A-115 I-7 II-7 A-156 1-12 II-9
A-75 I-3 II-5 A-116 I-8 II-7 A-157 1-13 II-9
A-76 I-4 II-5 A-117 I-9 II-7 A-158 1-14 II-9
A-77 I-5 II-5 A-118 1-10 II-7 A-159 1-15 II-9
A-78 I-6 II-5 A-119 1-11 II-7 A-160 1-16 II-9
A-79 I -7 II-5 A- 120 1-12 II-7 A-161 1-17 II-9
A-80 I-8 II-5 A-121 1-13 II-7 A-162 1-18 II-9
A-81 I-9 II-5 A- 122 1-14 II-7 A-163 1-1 11-10
A-82 1-10 II-5 A- 123 1-15 II-7 A-164 I-2 11-10
A-83 1-11 II-5 A- 124 1-16 II-7 A-165 I-3 11-10
A-84 1-12 II-5 A- 125 1-17 II-7 A-166 I-4 11-10
A-85 1-13 II-5 A- 126 1-18 II-7 A-167 I-5 11-10
A-86 1-14 II-5 A- 127 1-1 II-8 A-168 I-6 11-10
A-87 1-15 II-5 A- 128 I-2 II-8 A-169 I -7 11-10
A-88 1-16 II-5 A- 129 I-3 II-8 A-170 I-8 11-10
A-89 1-17 II-5 A- 130 I-4 II-8 A-171 I-9 11-10
A-90 1-18 II-5 A-131 I-5 II-8 A-172 1-10 11-10
A-91 1-1 II-6 A- 132 I-6 II-8 A-173 1-11 11-10
A-92 I-2 II-6 A- 133 I-7 II-8 A-174 1-12 11-10
A-93 I-3 II-6 A- 134 I-8 II-8 A-175 1-13 11-10
A-94 I-4 II-6 A- 135 I-9 II-8 A-176 1-14 11-10
A-95 I-5 II-6 A- 136 1-10 II-8 A-177 1-15 11-10
A-96 I-6 II-6 A- 137 1-11 II-8 A-178 1-16 11-10
A-97 I -7 II-6 A- 138 1-12 II-8 A-179 1-17 11-10
A-98 I-8 II-6 A- 139 1-13 II-8 A-180 1-18 11-10 No. I II No. I II No. I II
A-181 1-1 11-11 A-205 I-7 11-12 A-229 1-13 11-13
A-182 I-2 11-11 A-206 I-8 11-12 A-230 1-14 11-13
A-183 I-3 11-11 A-207 I-9 11-12 A-231 1-15 11-13
A-184 I-4 11-11 A-208 1-10 11-12 A-232 1-16 11-13
A-185 I-5 11-11 A-209 1-11 11-12 A-233 1-17 11-13
A-186 I-6 11-11 A-210 1-12 11-12 A-234 1-18 11-13
A-187 I -7 11-11 A-211 1-13 11-12 A-235 1-1 11-14
A-188 I-8 11-11 A-212 1-14 11-12 A-236 I-2 11-14
A-189 I-9 11-11 A-213 1-15 11-12 A-237 I-3 11-14
A-190 1-10 11-11 A-214 1-16 11-12 A-238 I-4 11-14
A-191 1-11 11-11 A-215 1-17 11-12 A-239 I-5 11-14
A-192 1-12 11-11 A-216 1-18 11-12 A-240 I-6 11-14
A-193 1-13 11-11 A-217 1-1 11-13 A-241 I -7 11-14
A-194 1-14 11-11 A-218 I-2 11-13 A-242 I-8 11-14
A-195 1-15 11-11 A-219 I-3 11-13 A-243 I-9 11-14
A-196 1-16 11-11 A-220 I-4 11-13 A-244 1-10 11-14
A-197 1-17 11-11 A-221 I-5 11-13 A-245 1-11 11-14
A-198 1-18 11-11 A-222 I-6 11-13 A-246 1-12 11-14
A-199 1-1 11-12 A-223 I-7 11-13 A-247 1-13 11-14
A-200 I-2 11-12 A-224 I-8 11-13 A-248 1-14 11-14
A-201 I-3 11-12 A-225 I-9 11-13 A-249 1-15 11-14
A-202 I-4 11-12 A-226 1-10 11-13 A-250 1-16 11-14
A-203 I-5 11-12 A-227 1-11 11-13 A-251 1-17 11-14
A-204 I-6 11-12 A-228 1-12 11-13 A-252 1-18 11-14
The mixtures A-1 to A-252 are preferably binary mixtures.
In one embodiment, the mixtures A-199 to A-252 are preferred, e.g. the mixtures A-199 to A- 216, or A-217 to A-234, or A-235 to A-252 may be particularly preferred.
Furthermore, the following mixtures of compounds I and biopesticide strains lla, as in Table B are preferred and represent embodiments of the invention:
Table B
No. I lla No. I lla No. I lla
B-1 1-1 lla-1 B-8 I-8 lla-1 B-15 1-15 lla-1
B-2 I-2 lla-1 B-9 I-9 lla-1 B-16 1-16 lla-1
B-3 I-3 lla-1 B-10 1-10 lla-1 B-17 1-17 lla-1
B-4 I-4 lla-1 B-11 1-11 lla-1 B-18 1-18 lla-1
B-5 I-5 lla-1 B-12 1-12 lla-1 B-19 1-1 lla-2
B-6 I-6 lla-1 B-13 1-13 lla-1 B-20 I-2 lla-2
B-7 I -7 lla-1 B-14 1-14 lla-1 B-21 I-3 lla-2 No. I 11 No. I 11 No. I 113
B-22 I-4 lla-2 B-63 I-9 lla-4 B-104 1-14 lla-6
B-23 I-5 lla-2 B-64 1-10 lla-4 B-105 1-15 lla-6
B-24 I-6 lla-2 B-65 1-1 1 lla-4 B-106 1-16 lla-6
B-25 I -7 lla-2 B-66 1-12 lla-4 B-107 1-17 lla-6
B-26 I-8 lla-2 B-67 1-13 lla-4 B-108 1-18 lla-6
B-27 I-9 lla-2 B-68 1-14 lla-4 B-109 1-1 lla-7
B-28 1-10 lla-2 B-69 1-15 lla-4 B-1 10 I-2 lla-7
B-29 1-1 1 lla-2 B-70 1-16 lla-4 B-1 1 1 I-3 lla-7
B-30 1-12 lla-2 B-71 1-17 lla-4 B-1 12 I-4 lla-7
B-31 1-13 lla-2 B-72 1-18 lla-4 B-1 13 I-5 lla-7
B-32 1-14 lla-2 B-73 1-1 lla-5 B-1 14 I-6 lla-7
B-33 1-15 lla-2 B-74 I-2 lla-5 B-1 15 I -7 lla-7
B-34 1-16 lla-2 B-75 I-3 lla-5 B-1 16 I-8 lla-7
B-35 1-17 lla-2 B-76 I-4 lla-5 B-1 17 I-9 lla-7
B-36 1-18 lla-2 B-77 I-5 lla-5 B-1 18 1-10 lla-7
B-37 1-1 lla-3 B-78 I-6 lla-5 B-1 19 1-1 1 lla-7
B-38 I-2 lla-3 B-79 I-7 lla-5 B-120 1-12 lla-7
B-39 I-3 lla-3 B-80 I-8 lla-5 B-121 1-13 lla-7
B-40 I-4 lla-3 B-81 I-9 lla-5 B-122 1-14 lla-7
B-41 I-5 lla-3 B-82 1-10 lla-5 B-123 1-15 lla-7
B-42 I-6 lla-3 B-83 1-1 1 lla-5 B-124 1-16 lla-7
B-43 I -7 lla-3 B-84 1-12 lla-5 B-125 1-17 lla-7
B-44 I-8 lla-3 B-85 1-13 lla-5 B-126 1-18 lla-7
B-45 I-9 lla-3 B-86 1-14 lla-5 B-127 1-1 lla-8
B-46 1-10 lla-3 B-87 1-15 lla-5 B-128 I-2 lla-8
B-47 1-1 1 lla-3 B-88 1-16 lla-5 B-129 I-3 lla-8
B-48 1-12 lla-3 B-89 1-17 lla-5 B-130 I-4 lla-8
B-49 1-13 lla-3 B-90 1-18 lla-5 B-131 I-5 lla-8
B-50 1-14 lla-3 B-91 1-1 lla-6 B-132 I-6 lla-8
B-51 1-15 lla-3 B-92 I-2 lla-6 B-133 I -7 lla-8
B-52 1-16 lla-3 B-93 I-3 lla-6 B-134 I-8 lla-8
B-53 1-17 lla-3 B-94 I-4 lla-6 B-135 I-9 lla-8
B-54 1-18 lla-3 B-95 I-5 lla-6 B-136 1-10 lla-8
B-55 1-1 lla-4 B-96 I-6 lla-6 B-137 1-1 1 lla-8
B-56 I-2 lla-4 B-97 I-7 lla-6 B-138 1-12 lla-8
B-57 I-3 lla-4 B-98 I-8 lla-6 B-139 1-13 lla-8
B-58 I-4 lla-4 B-99 I-9 lla-6 B-140 1-14 lla-8
B-59 I-5 lla-4 B-100 1-10 lla-6 B-141 1-15 lla-8
B-60 I-6 lla-4 B-101 1-1 1 lla-6 B-142 1-16 lla-8
B-61 I -7 lla-4 B-102 1-12 lla-6 B-143 1-17 lla-8
B-62 I-8 lla-4 B-103 1-13 lla-6 B-144 1-18 lla-8 No. I 11 No. I 11 No. I 113
B-145 1-1 lla-9 B-163 1-1 lla-10 B-181 1-1 lla-1 1
B-146 I-2 lla-9 B-164 I-2 lla-10 B-182 I-2 lla-1 1
B-147 I-3 lla-9 B-165 I-3 lla-10 B-183 I-3 lla-1 1
B-148 I-4 lla-9 B-166 I-4 lla-10 B-184 I-4 lla-1 1
B-149 I-5 lla-9 B-167 I-5 lla-10 B-185 I-5 lla-1 1
B-150 I-6 lla-9 B-168 I-6 lla-10 B-186 I-6 lla-1 1
B-151 I -7 lla-9 B-169 I-7 lla-10 B-187 I -7 lla-1 1
B-152 I-8 lla-9 B-170 I-8 lla-10 B-188 I-8 lla-1 1
B-153 I-9 lla-9 B-171 I-9 lla-10 B-189 I-9 lla-1 1
B-154 1-10 lla-9 B-172 1-10 lla-10 B-190 1-10 lla-1 1
B-155 1-1 1 lla-9 B-173 1-1 1 lla-10 B-191 1-1 1 lla-1 1
B-156 1-12 lla-9 B-174 1-12 lla-10 B-192 1-12 lla-1 1
B-157 1-13 lla-9 B-175 1-13 lla-10 B-193 1-13 lla-1 1
B-158 1-14 lla-9 B-176 1-14 lla-10 B-194 1-14 lla-1 1
B-159 1-15 lla-9 B-177 1-15 lla-10 B-195 1-15 lla-1 1
B-160 1-16 lla-9 B-178 1-16 lla-10 B-196 1-16 lla-1 1
B-161 1-17 lla-9 B-179 1-17 lla-10 B-197 1-17 lla-1 1
B-162 1-18 lla-9 B-180 1-18 lla-10 B-198 1-18 lla-1 1
The mixtures B-1 to B-198 are preferably binary mixtures.
In one embodiment, the mixtures B-145 to B-198 are preferred, e.g. the mixtures B-145 to B- 162, or B-163 to B-180, or B-181 to B-198 may be particularly preferred.
According to the invention, the solid material (dry matter) of the biopesticides (with the exception of oils such as 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 present invention, the weight ratios and percentages used herein for a biological extract such as 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 calclulate the total weight of the respective active component with the following equation that 1 x 1010 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 (entomopathogenic) nematode biopesticides, such as
Steinernema feltiae.
As already indicated above, component 1 ) and component 2) of the mixtures of the invention are present in synergistically effective amounts. In one embodiment, component 1) and component 2) of the mixtures of the invention are present in a total weight ratio of from 100:1 to 1 :100, wherein the total weight of component 2) is based on the amount of the solid material (dry mater) of component 2).
In the binary mixtures and compositions according to the invention the weight ratio of the component 1 ) and the component 2) generally depends from the properties of the active components used, usually it is in the range of from 1:10,000 to 10,000:1, often it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1, even more preferably in the range of from 1:4 to 4:1 and in particular in the range of from 1:2 to 2:1.
According to further embodiments of the binary mixtures and compositions, the weight ratio of the component 1) and the component 2) usually is in the range of from 1000:1 to 1:1, often in the range of from 100: 1 to 1:1, regularly in the range of from 50:1 to 1:1, preferably in the range of from 20:1 to 1:1, more preferably in the range of from 10:1 to 1:1, even more preferably in the range of from 4:1 to 1:1 and in particular in the range of from 2:1 to 1:1.
According to further embodiments of the mixtures and compositions, the weight ratio of the component 1) and the component 2) usually is in the range of from 20,000:1 to 1:10, often in the range of from 10,000:1 to 1:1, regularly in the range of from 5,000:1 to 5:1, preferably in the range of from 5,000:1 to 10:1, more preferably in the range of from 2,000:1 to 30:1, even more preferably in the range of from 2,000:1 to 100:1 and in particular in the range of from 1,000:1 to 100:1.
According to a further embodiments of the binary mixtures and compositions, the weight ratio of the component 1) and the component 2) usually is in the range of from 1:1 to 1:1000, often in the range of from 1:1 to 1:100, regularly in the range of from 1:1 to 1:50, preferably in the range of from 1:1 to 1:20, more preferably in the range of from 1:1 to 1:10, even more preferably in the range of from 1:1 to 1:4 and in particular in the range of from 1:1 to 1:2.
According to further embodiments of the mixtures and compositions, the weight ratio of the component 1) and the component 2) usually is in the range of from 10:1 to 1:20,000, often in the range of from 1:1 to 1:10,000, regularly in the range of from 1:5 to 1:5,000, preferably in the range of from 1:10 to 1:5,000, more preferably in the range of from 1:30 to 1:2,000, even more preferably in the range of from 1 : 100 to 1 :2,000 to and in particular in the range of from 1 : 100 to 1:1,000.
In the ternary mixtures, i.e. compositions according to the invention comprising the component 1) and component 2) and a compound III (component 3), the weight ratio of component 1) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 : 100 to 100:1, regularly in the range of from 1 :50 to 50: 1 , preferably in the range of from 1 :20 to 20: 1 , more preferably in the range of from 1 : 10 to 10:1 and in particular in the range of from 1:4 to 4:1, and the weight ratio of component 1) and component 3) usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1 :4 to 4: 1.
Any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the component 1).
These ratios are also suitable for inventive mixtures applied by seed treatment. When mixtures comprising microbial pesticides are employed in crop protection, the application rates preferably range from about 1 x 106 to 5 x 1015 (or more) CFU/ha, preferably from about 1 x 108 to about 1 x 1013 CFU/ha, and even more preferably from about 1 x 109 to about 1 x 1012 CFU/ha. In the case of (entomopathogenic) nematodes as microbial pesticides (e. g. Steinernema feltiae), the application rates preferably range inform about 1 x 105 to 1 x 1012 (or more), more preferably from 1 x 108 to 1 x 1011, even more preferably from 5 x 108 to 1 x 1010 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 with respect to plant propagation material preferably range from about 1 x 106 to 1 x 1012 (or more) CFU/seed. Preferably, the concentration is about 1 x 106 to about 1 x 109 CFU/seed. In the case of the microbial pesticides II, the application rates with respect to plant propagation material also preferably range from about 1 x 107 to 1 x 1014 (or more) CFU per 100 kg of seed, preferably from 1 x 109 to about 1 x 1012 CFU per 100 kg of seed.
In one embodiment, the mixtures of the invention, in particular the mixtures A-1 to A-108 or B-
1 to B-108, further comprise as active component 3) a further active compound III, which is selected from insecticides or fungicides.
The insecticides, which are hereinafter described by common names, are commercially available and may be found in The Pesticide Manual, 16th Edition, C. MacBean, British Crop
Protection Council (2013) among other publications. The online Pesticide Manual is updated regularly and is accessible through http://bcpcdata.com/pesticide-manual.html. Another online data base for pesticides providing the ISO common names is
http://www.alanwood.net/pesticides.
he fungicides, which are hereinafter described by common names, are commercially available and may be found in the database http://www.alanwood.net/pesticides.
In one embodiment, the mixtures of the invention further comprise as active component 3) a further active compound III, which is an insecticide, wherein said insecticide is selected from the group consisting of fipronil, clothianidin, thiamethoxam, acetamiprid, dinotefuran, imidacloprid, thiacloprid, sulfoxaflor, methiocarb, tefluthrin, bifenthrin, cypermethrin, alphacypermethrin, spinosad, cyantraniliprole, chlorantraniliprole, triflumezopyrim, flupyradifurone, abamectin, thiodicarb, tetraniliprole, tioxazafen, and broflanilide.
In another embodiment, the mixtures of the invention further comprise as active component 3) a further active compound III, which is a fungicide, wherein said fungicide is selected from the group consisting of azoxstrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, sedaxane, penthiopyrad, penflufen, fluopyram, fluxapyroxad, boscalid, oxathiapiprolin, metalaxyl, metalaxyl-M, ethaboxam, dimethomorph, cyproconazole, difenoconazole, prothioconazole, flutriafol, thiabendazole, ipconazole, tebuconazole, triadimenol, prochloraz, fluquinconazole, triticonazole, fludioxonil, carboxin, silthiofarm, ziram, thiram, carbendazim, thiophanate methyl, fenamidone, hymexazol, and fluazinam. If the active compound III is an insecticide, said insecticide is preferably selected from the insecticides as defined in the following table Ilia. The insecticides as listed in table Ilia are in the following referred to as insecticides llla-1 to ll la-22.
Figure imgf000029_0002
Figure imgf000029_0001
If the active compound III is a fungicide, said fungicide is preferably selected from the fungicides as defined in the following table lllb. The fungicides as listed in table lllb are in the following referred to as fungicides lllb-1 to lllb-36.
Table lllb
No fungicide No fungicide lllb-1 azoxstrobin lllb-19 flutriafol lllb-2 trifloxystrobin lllb-20 thiabendazole lllb-3 picoxystrobin lllb-21 ipconazole lllb-4 pyraclostrobin lllb-22 tebuconazole lllb-5 sedaxane lllb-23 triadimenol lllb-6 penthiopyrad lllb-24 prochloraz lllb-7 penflufen lllb-25 fluquinconazole lllb-8 fluopyram lllb-26 triticonazole lllb-9 fluxapyroxad lllb-27 fludioxonil lllb-10 boscalid lllb-28 carboxin lllb-1 1 oxathiapiprolin lllb-29 silthiofarm lllb-12 metalaxyl lllb-30 ziram
lllb-13 metalaxyl-M lllb-31 thiram
lllb-14 ethaboxam lllb-32 carbendazim lllb-15 dimethomorph lllb-33 thiophanate methyl lllb-16 cyproconazole lllb-34 fenamidone lllb-17 difenoconazole lllb-35 hymexazol lllb-18 prothioconazole lllb-36 fluazinam In one embodiment, the present invention relates to mixtures, which comprise at least one compound of formula I, which is selected from the compounds 1-1 to 1-18, as component 1 ), and at least one biopesticide II, which is selected from the biopesticides 11-1 to 11-14, in particular from the biopesticide strains lla-1 to lla-1 1 , and at least one further active compound III, which may be selected from the insecticides llla-1 to llla-23, or the fungicides lllb-1 to lllb-36.
Such mixtures are preferably ternary mixture comprising one compound of formula I, which is selected from the compounds 1-1 to 1-18, as component 1 ), and one biopesticide II, which is selected from the biopesticides 11-1 to 11-14, in particular from the biopesticide strains lla-1 to lla- 1 1 , and one further active compound III, which may be selected from the insecticides llla-1 to llla-23, or the fungicides lllb-1 to lllb-36.
Preference is given to the pesticidal mixtures compiled in the tables below.
Table 1 Pesticidal mixtures, which comprise compound 1-1 , and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 2 Pesticidal mixtures, which comprise compound I-2, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 3 Pesticidal mixtures, which comprise compound I-3, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 4 Pesticidal mixtures, which comprise compound I-4, and in which combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 5 Pesticidal mixtures, which comprise compound I-5, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 6 Pesticidal mixtures, which comprise compound I-6, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 7 Pesticidal mixtures, which comprise compound I-7, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 8 Pesticidal mixtures, which comprise compound I-8, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 9 Pesticidal mixtures, which comprise compound I-9, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 10 Pesticidal mixtures, which comprise compound 1-10, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M Table 1 1 Pesticidal mixtures, which comprise compound 1-1 1 , and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain I la with an active compound III according to one row of Table M
Table 12 Pesticidal mixtures, which comprise compound 1-12, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 13 Pesticidal mixtures, which comprise compound 1-13, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 14 Pesticidal mixtures, which comprise compound 1-14, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 15 Pesticidal mixtures, which comprise compound 1-15, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 16 Pesticidal mixtures, which comprise compound 1-16, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 17 Pesticidal mixtures, which comprise compound 1-17, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table 18 Pesticidal mixtures, which comprise compound 1-18, and in which the combination of components 2) and 3) corresponds in each case to the combination of a biopesticide II or biopesticide strain lla with an active compound III according to one row of Table M
Table M
No. ll/lla III No. ll/lla III No. ll/lla III
M-1 11-1 llla-1 M-17 M-3 llla-2 M-33 M-5 llla-3
M-2 M-2 llla-1 M-18 M-4 llla-2 M-34 M-6 llla-3
M-3 M-3 llla-1 M-19 M-5 llla-2 M-35 M-7 llla-3
M-4 M-4 llla-1 M-20 M-6 llla-2 M-36 M-8 llla-3
M-5 M-5 llla-1 M-21 M-7 llla-2 M-37 M-9 llla-3
M-6 M-6 llla-1 M-22 M-8 llla-2 M-38 11-10 llla-3
M-7 M-7 llla-1 M-23 M-9 llla-2 M-39 11-1 1 llla-3
M-8 M-8 llla-1 M-24 11-10 llla-2 M-40 11-12 llla-3
M-9 M-9 llla-1 M-25 11-1 1 llla-2 M-41 11-13 llla-3
M-10 11-10 llla-1 M-26 11-12 llla-2 M-42 11-14 llla-3
M-1 1 11-1 1 llla-1 M-27 11-13 llla-2 M-43 11-1 llla-4
M-12 11-12 llla-1 M-28 11-14 llla-2 M-44 M-2 llla-4
M-13 11-13 llla-1 M-29 11-1 llla-3 M-45 M-3 llla-4
M-14 11-14 llla-1 M-30 M-2 llla-3 M-46 M-4 llla-4
M-15 11-1 llla-2 M-31 M-3 llla-3 M-47 M-5 llla-4
M-16 M-2 llla-2 M-32 M-4 llla-3 M-48 M-6 llla-4 No. ll/lla III No. ll/lla III No. ll/lla III
M-49 II-7 llla-4 M-90 II-6 llla-7 M-131 II-5 llla-10
M-50 II-8 llla-4 M-91 II-7 llla-7 M-132 II-6 llla-10
M-51 II-9 llla-4 M-92 II-8 llla-7 M-133 II-7 llla-10
M-52 11-10 llla-4 M-93 II-9 llla-7 M-134 II-8 llla-10
M-53 11-1 1 llla-4 M-94 11-10 llla-7 M-135 II-9 llla-10
M-54 11-12 llla-4 M-95 11-1 1 llla-7 M-136 11-10 llla-10
M-55 11-13 llla-4 M-96 11-12 llla-7 M-137 11-1 1 llla-10
M-56 11-14 llla-4 M-97 11-13 llla-7 M-138 11-12 llla-10
M-57 11-1 llla-5 M-98 11-14 llla-7 M-139 11-13 llla-10
M-58 II-2 llla-5 M-99 11-1 llla-8 M-140 11-14 llla-10
M-59 II-3 llla-5 M-100 II-2 llla-8 M-141 11-1 llla-1 1
M-60 II-4 llla-5 M-101 II-3 llla-8 M-142 II-2 llla-1 1
M-61 II-5 llla-5 M-102 II-4 llla-8 M-143 II-3 llla-1 1
M-62 II-6 llla-5 M-103 II-5 llla-8 M-144 II-4 llla-1 1
M-63 II-7 llla-5 M-104 II-6 llla-8 M-145 II-5 llla-1 1
M-64 II-8 llla-5 M-105 II-7 llla-8 M-146 II-6 llla-1 1
M-65 II-9 llla-5 M-106 II-8 llla-8 M-147 II-7 llla-1 1
M-66 11-10 llla-5 M-107 II-9 llla-8 M-148 II-8 llla-1 1
M-67 11-1 1 llla-5 M-108 11-10 llla-8 M-149 II-9 llla-1 1
M-68 11-12 llla-5 M-109 11-1 1 llla-8 M-150 11-10 llla-1 1
M-69 11-13 llla-5 M-1 10 11-12 llla-8 M-151 11-1 1 llla-1 1
M-70 11-14 llla-5 M-1 1 1 11-13 llla-8 M-152 11-12 llla-1 1
M-71 11-1 llla-6 M-1 12 11-14 llla-8 M-153 11-13 llla-1 1
M-72 II-2 llla-6 M-1 13 11-1 llla-9 M-154 11-14 llla-1 1
M-73 II-3 llla-6 M-1 14 II-2 llla-9 M-155 11-1 llla-12
M-74 II-4 llla-6 M-1 15 II-3 llla-9 M-156 II-2 llla-12
M-75 II-5 llla-6 M-1 16 II-4 llla-9 M-157 II-3 llla-12
M-76 II-6 llla-6 M-1 17 II-5 llla-9 M-158 II-4 llla-12
M-77 II-7 llla-6 M-1 18 II-6 llla-9 M-159 II-5 llla-12
M-78 II-8 llla-6 M-1 19 II-7 llla-9 M-160 II-6 llla-12
M-79 II-9 llla-6 M-120 II-8 llla-9 M-161 II-7 llla-12
M-80 11-10 llla-6 M-121 II-9 llla-9 M-162 II-8 llla-12
M-81 11-1 1 llla-6 M-122 11-10 llla-9 M-163 II-9 llla-12
M-82 11-12 llla-6 M-123 11-1 1 llla-9 M-164 11-10 llla-12
M-83 11-13 llla-6 M-124 11-12 llla-9 M-165 11-1 1 llla-12
M-84 11-14 llla-6 M-125 11-13 llla-9 M-166 11-12 llla-12
M-85 11-1 llla-7 M-126 11-14 llla-9 M-167 11-13 llla-12
M-86 II-2 llla-7 M-127 11-1 llla-10 M-168 11-14 llla-12
M-87 II-3 llla-7 M-128 II-2 llla-10 M-169 11-1 3
M-88 II-4 llla-7 M-129 II-3 llla-10 M-170 II-2 llla-13
M-89 II-5 llla-7 M-130 II-4 llla-10 M-171 II-3 llla-13 No. ll/lla III No. ll/lla III No. ll/lla III
M-172 II-4 llla-13 M-213 II-3 llla-16 M-254 II-2 llla-19
M-173 II-5 llla-13 M-214 II-4 llla-16 M-255 II-3 llla-19
M-174 II-6 llla-13 M-215 II-5 llla-16 M-256 II-4 llla-19
M-175 II-7 llla-13 M-216 II-6 llla-16 M-257 II-5 llla-19
M-176 II-8 llla-13 M-217 II-7 llla-16 M-258 II-6 llla-19
M-177 II-9 llla-13 M-218 II-8 llla-16 M-259 II-7 llla-19
M-178 11-10 llla-13 M-219 II-9 llla-16 M-260 II-8 llla-19
M-179 11-1 1 llla-13 M-220 11-10 llla-16 M-261 II-9 llla-19
M-180 11-12 llla-13 M-221 11-1 1 llla-16 M-262 11-10 llla-19
M-181 11-13 llla-13 M-222 11-12 llla-16 M-263 11-1 1 llla-19
M-182 11-14 llla-13 M-223 11-13 llla-16 M-264 11-12 llla-19
M-183 11-1 llla-14 M-224 11-14 llla-16 M-265 11-13 llla-19
M-184 II-2 llla-14 M-225 11-1 llla-17 M-266 11-14 llla-19
M-185 II-3 llla-14 M-226 II-2 llla-17 M-267 11-1 llla-20
M-186 II-4 llla-14 M-227 II-3 llla-17 M-268 II-2 llla-20
M-187 II-5 llla-14 M-228 II-4 llla-17 M-269 II-3 llla-20
M-188 II-6 llla-14 M-229 II-5 llla-17 M-270 II-4 llla-20
M-189 II-7 llla-14 M-230 II-6 llla-17 M-271 II-5 llla-20
M-190 II-8 llla-14 M-231 II-7 llla-17 M-272 II-6 llla-20
M-191 II-9 llla-14 M-232 II-8 llla-17 M-273 II-7 llla-20
M-192 11-10 llla-14 M-233 II-9 llla-17 M-274 II-8 llla-20
M-193 11-1 1 llla-14 M-234 11-10 llla-17 M-275 II-9 llla-20
M-194 11-12 llla-14 M-235 11-1 1 llla-17 M-276 11-10 llla-20
M-195 11-13 llla-14 M-236 11-12 llla-17 M-277 11-1 1 llla-20
M-196 11-14 llla-14 M-237 11-13 llla-17 M-278 11-12 llla-20
M-197 11-1 llla-15 M-238 11-14 llla-17 M-279 11-13 llla-20
M-198 II-2 llla-15 M-239 11-1 llla-18 M-280 11-14 llla-20
M-199 II-3 llla-15 M-240 II-2 llla-18 M-281 11-1 llla-21
M-200 II-4 llla-15 M-241 II-3 llla-18 M-282 II-2 llla-21
M-201 II-5 llla-15 M-242 II-4 llla-18 M-283 II-3 llla-21
M-202 II-6 llla-15 M-243 II-5 llla-18 M-284 II-4 llla-21
M-203 II-7 llla-15 M-244 II-6 llla-18 M-285 II-5 llla-21
M-204 II-8 llla-15 M-245 II-7 llla-18 M-286 II-6 llla-21
M-205 II-9 llla-15 M-246 II-8 llla-18 M-287 II-7 llla-21
M-206 11-10 llla-15 M-247 II-9 llla-18 M-288 II-8 llla-21
M-207 11-1 1 llla-15 M-248 11-10 llla-18 M-289 II-9 llla-21
M-208 11-12 llla-15 M-249 11-1 1 llla-18 M-290 11-10 llla-21
M-209 11-13 llla-15 M-250 11-12 llla-18 M-291 11-1 1 llla-21
M-210 11-14 llla-15 M-251 11-13 llla-18 M-292 11-12 llla-21
M-21 1 11-1 llla-16 M-252 11-14 llla-18 M-293 11-13 llla-21
M-212 II-2 llla-16 M-253 11-1 llla-19 M-294 11-14 llla-21 No. ll/lla III No. ll/lla III No. ll/lla III
M-295 11-1 llla-22 M-336 11-14 lllb-1 M-377 11-13 lllb-4
M-296 II-2 llla-22 M-337 11-1 lllb-2 M-378 11-14 lllb-4
M-297 II-3 llla-22 M-338 II-2 lllb-2 M-379 11-1 lllb-5
M-298 II-4 llla-22 M-339 II-3 lllb-2 M-380 II-2 lllb-5
M-299 II-5 llla-22 M-340 II-4 lllb-2 M-381 II-3 lllb-5
M-300 II-6 llla-22 M-341 II-5 lllb-2 M-382 II-4 lllb-5
M-301 II-7 llla-22 M-342 II-6 lllb-2 M-383 II-5 lllb-5
M-302 II-8 llla-22 M-343 II-7 lllb-2 M-384 II-6 lllb-5
M-303 II-9 llla-22 M-344 II-8 lllb-2 M-385 II-7 lllb-5
M-304 11-10 llla-22 M-345 II-9 lllb-2 M-386 II-8 lllb-5
M-305 11-1 1 llla-22 M-346 11-10 lllb-2 M-387 II-9 lllb-5
M-306 11-12 llla-22 M-347 11-1 1 lllb-2 M-388 11-10 lllb-5
M-307 11-13 llla-22 M-348 11-12 lllb-2 M-389 11-1 1 lllb-5
M-308 11-14 llla-22 M-349 11-13 lllb-2 M-390 11-12 lllb-5
M-309 11-1 llla-23 M-350 11-14 lllb-2 M-391 11-13 lllb-5
M-310 II-2 llla-23 M-351 11-1 lllb-3 M-392 11-14 lllb-5
M-31 1 II-3 llla-23 M-352 II-2 lllb-3 M-393 11-1 lllb-6
M-312 II-4 llla-23 M-353 II-3 lllb-3 M-394 II-2 lllb-6
M-313 II-5 llla-23 M-354 II-4 lllb-3 M-395 II-3 lllb-6
M-314 II-6 llla-23 M-355 II-5 lllb-3 M-396 II-4 lllb-6
M-315 II-7 llla-23 M-356 II-6 lllb-3 M-397 II-5 lllb-6
M-316 II-8 llla-23 M-357 II-7 lllb-3 M-398 II-6 lllb-6
M-317 II-9 llla-23 M-358 II-8 lllb-3 M-399 II-7 lllb-6
M-318 11-10 llla-23 M-359 II-9 lllb-3 M-400 II-8 lllb-6
M-319 11-1 1 llla-23 M-360 11-10 lllb-3 M-401 II-9 lllb-6
M-320 11-12 llla-23 M-361 11-1 1 lllb-3 M-402 11-10 lllb-6
M-321 11-13 llla-23 M-362 11-12 lllb-3 M-403 11-1 1 lllb-6
M-322 11-14 llla-23 M-363 11-13 lllb-3 M-404 11-12 lllb-6
M-323 11-1 lllb-1 M-364 11-14 lllb-3 M-405 11-13 lllb-6
M-324 II-2 lllb-1 M-365 11-1 lllb-4 M-406 11-14 lllb-6
M-325 II-3 lllb-1 M-366 II-2 lllb-4 M-407 11-1 lllb-7
M-326 II-4 lllb-1 M-367 II-3 lllb-4 M-408 II-2 lllb-7
M-327 II-5 lllb-1 M-368 II-4 lllb-4 M-409 II-3 lllb-7
M-328 II-6 lllb-1 M-369 II-5 lllb-4 M-410 II-4 lllb-7
M-329 II-7 lllb-1 M-370 II-6 lllb-4 M-41 1 II-5 lllb-7
M-330 II-8 lllb-1 M-371 II-7 lllb-4 M-412 II-6 lllb-7
M-331 II-9 lllb-1 M-372 II-8 lllb-4 M-413 II-7 lllb-7
M-332 11-10 lllb-1 M-373 II-9 lllb-4 M-414 II-8 lllb-7
M-333 11-1 1 lllb-1 M-374 11-10 lllb-4 M-415 II-9 lllb-7
M-334 11-12 lllb-1 M-375 11-1 1 lllb-4 M-416 11-10 lllb-7
M-335 11-13 lllb-1 M-376 11-12 lllb-4 M-417 11-1 1 lllb-7 No. ll/lla III No. ll/lla III No. ll/lla III
M-418 11-12 lllb-7 M-459 11-1 1 lllb-10 M-500 11-10 lllb-13
M-419 11-13 lllb-7 M-460 11-12 lllb-10 M-501 11-1 1 lllb-13
M-420 11-14 lllb-7 M-461 11-13 lllb-10 M-502 11-12 lllb-13
M-421 11-1 lllb-8 M-462 11-14 lllb-10 M-503 11-13 lllb-13
M-422 II-2 lllb-8 M-463 11-1 lllb-1 1 M-504 11-14 lllb-13
M-423 II-3 lllb-8 M-464 II-2 lllb-1 1 M-505 11-1 lllb-14
M-424 II-4 lllb-8 M-465 II-3 lllb-1 1 M-506 II-2 lllb-14
M-425 II-5 lllb-8 M-466 II-4 lllb-1 1 M-507 II-3 lllb-14
M-426 II-6 lllb-8 M-467 II-5 lllb-1 1 M-508 II-4 lllb-14
M-427 II-7 lllb-8 M-468 II-6 lllb-1 1 M-509 II-5 lllb-14
M-428 II-8 lllb-8 M-469 II-7 lllb-1 1 M-510 II-6 lllb-14
M-429 II-9 lllb-8 M-470 II-8 lllb-1 1 M-51 1 II-7 lllb-14
M-430 11-10 lllb-8 M-471 II-9 lllb-1 1 M-512 II-8 lllb-14
M-431 11-1 1 lllb-8 M-472 11-10 lllb-1 1 M-513 II-9 lllb-14
M-432 11-12 lllb-8 M-473 11-1 1 lllb-1 1 M-514 11-10 lllb-14
M-433 11-13 lllb-8 M-474 11-12 lllb-1 1 M-515 11-1 1 lllb-14
M-434 11-14 lllb-8 M-475 11-13 lllb-1 1 M-516 11-12 lllb-14
M-435 11-1 lllb-9 M-476 11-14 lllb-1 1 M-517 11-13 lllb-14
M-436 II-2 lllb-9 M-477 11-1 lllb-12 M-518 11-14 lllb-14
M-437 II-3 lllb-9 M-478 II-2 lllb-12 M-519 11-1 lllb-15
M-438 II-4 lllb-9 M-479 II-3 lllb-12 M-520 II-2 lllb-15
M-439 II-5 lllb-9 M-480 II-4 lllb-12 M-521 II-3 lllb-15
M-440 II-6 lllb-9 M-481 II-5 lllb-12 M-522 II-4 lllb-15
M-441 II-7 lllb-9 M-482 II-6 lllb-12 M-523 II-5 lllb-15
M-442 II-8 lllb-9 M-483 II-7 lllb-12 M-524 II-6 lllb-15
M-443 II-9 lllb-9 M-484 II-8 lllb-12 M-525 II-7 lllb-15
M-444 11-10 lllb-9 M-485 II-9 lllb-12 M-526 II-8 lllb-15
M-445 11-1 1 lllb-9 M-486 11-10 lllb-12 M-527 II-9 lllb-15
M-446 11-12 lllb-9 M-487 11-1 1 lllb-12 M-528 11-10 lllb-15
M-447 11-13 lllb-9 M-488 11-12 lllb-12 M-529 11-1 1 lllb-15
M-448 11-14 lllb-9 M-489 11-13 lllb-12 M-530 11-12 lllb-15
M-449 11-1 lllb-10 M-490 11-14 lllb-12 M-531 11-13 lllb-15
M-450 II-2 lllb-10 M-491 11-1 lllb-13 M-532 11-14 lllb-15
M-451 II-3 lllb-10 M-492 II-2 lllb-13 M-533 11-1 lllb-16
M-452 II-4 lllb-10 M-493 II-3 lllb-13 M-534 II-2 lllb-16
M-453 II-5 lllb-10 M-494 II-4 lllb-13 M-535 II-3 lllb-16
M-454 II-6 lllb-10 M-495 II-5 lllb-13 M-536 II-4 lllb-16
M-455 II-7 lllb-10 M-496 II-6 lllb-13 M-537 II-5 lllb-16
M-456 II-8 lllb-10 M-497 II-7 lllb-13 M-538 II-6 lllb-16
M-457 II-9 lllb-10 M-498 II-8 lllb-13 M-539 II-7 lllb-16
M-458 11-10 lllb-10 M-499 II-9 lllb-13 M-540 II-8 lllb-16 No. ll/lla III No. ll/lla III No. ll/lla III
M-541 II-9 lllb-16 M-582 II-8 lllb-19 M-623 II-7 lllb-22
M-542 11-10 lllb-16 M-583 II-9 lllb-19 M-624 II-8 lllb-22
M-543 11-1 1 lllb-16 M-584 11-10 lllb-19 M-625 II-9 lllb-22
M-544 11-12 lllb-16 M-585 11-1 1 lllb-19 M-626 11-10 lllb-22
M-545 11-13 lllb-16 M-586 11-12 lllb-19 M-627 11-1 1 lllb-22
M-546 11-14 lllb-16 M-587 11-13 lllb-19 M-628 11-12 lllb-22
M-547 11-1 lllb-17 M-588 11-14 lllb-19 M-629 11-13 lllb-22
M-548 II-2 lllb-17 M-589 11-1 lllb-20 M-630 11-14 lllb-22
M-549 II-3 lllb-17 M-590 II-2 lllb-20 M-631 11-1 lllb-23
M-550 II-4 lllb-17 M-591 II-3 lllb-20 M-632 II-2 lllb-23
M-551 II-5 lllb-17 M-592 II-4 lllb-20 M-633 II-3 lllb-23
M-552 II-6 lllb-17 M-593 II-5 lllb-20 M-634 II-4 lllb-23
M-553 II-7 lllb-17 M-594 II-6 lllb-20 M-635 II-5 lllb-23
M-554 II-8 lllb-17 M-595 II-7 lllb-20 M-636 II-6 lllb-23
M-555 II-9 lllb-17 M-596 II-8 lllb-20 M-637 II-7 lllb-23
M-556 11-10 lllb-17 M-597 II-9 lllb-20 M-638 II-8 lllb-23
M-557 11-1 1 lllb-17 M-598 11-10 lllb-20 M-639 II-9 lllb-23
M-558 11-12 lllb-17 M-599 11-1 1 lllb-20 M-640 11-10 lllb-23
M-559 11-13 lllb-17 M-600 11-12 lllb-20 M-641 11-1 1 lllb-23
M-560 11-14 lllb-17 M-601 11-13 lllb-20 M-642 11-12 lllb-23
M-561 11-1 lllb-18 M-602 11-14 lllb-20 M-643 11-13 lllb-23
M-562 II-2 lllb-18 M-603 11-1 lllb-21 M-644 11-14 lllb-23
M-563 II-3 lllb-18 M-604 II-2 lllb-21 M-645 11-1 lllb-24
M-564 II-4 lllb-18 M-605 II-3 lllb-21 M-646 II-2 lllb-24
M-565 II-5 lllb-18 M-606 II-4 lllb-21 M-647 II-3 lllb-24
M-566 II-6 lllb-18 M-607 II-5 lllb-21 M-648 II-4 lllb-24
M-567 II-7 lllb-18 M-608 II-6 lllb-21 M-649 II-5 lllb-24
M-568 II-8 lllb-18 M-609 II-7 lllb-21 M-650 II-6 lllb-24
M-569 II-9 lllb-18 M-610 II-8 lllb-21 M-651 II-7 lllb-24
M-570 11-10 lllb-18 M-61 1 II-9 lllb-21 M-652 II-8 lllb-24
M-571 11-1 1 lllb-18 M-612 11-10 lllb-21 M-653 II-9 lllb-24
M-572 11-12 lllb-18 M-613 11-1 1 lllb-21 M-654 11-10 lllb-24
M-573 11-13 lllb-18 M-614 11-12 lllb-21 M-655 11-1 1 lllb-24
M-574 11-14 lllb-18 M-615 11-13 lllb-21 M-656 11-12 lllb-24
M-575 11-1 lllb-19 M-616 11-14 lllb-21 M-657 11-13 lllb-24
M-576 II-2 lllb-19 M-617 11-1 lllb-22 M-658 11-14 lllb-24
M-577 II-3 lllb-19 M-618 II-2 lllb-22 M-659 11-1 lllb-25
M-578 II-4 lllb-19 M-619 II-3 lllb-22 M-660 II-2 lllb-25
M-579 II-5 lllb-19 M-620 II-4 lllb-22 M-661 II-3 lllb-25
M-580 II-6 lllb-19 M-621 II-5 lllb-22 M-662 II-4 lllb-25
M-581 II-7 lllb-19 M-622 II-6 lllb-22 M-663 II-5 lllb-25 No. ll/lla III No. ll/lla III No. ll/lla III
M-664 II-6 lllb-25 M-705 II-5 lllb-28 M-746 II-4 lllb-31
M-665 II-7 lllb-25 M-706 II-6 lllb-28 M-747 II-5 lllb-31
M-666 II-8 lllb-25 M-707 II-7 lllb-28 M-748 II-6 lllb-31
M-667 II-9 lllb-25 M-708 II-8 lllb-28 M-749 II-7 lllb-31
M-668 11-10 lllb-25 M-709 II-9 lllb-28 M-750 II-8 lllb-31
M-669 11-1 1 lllb-25 M-710 11-10 lllb-28 M-751 II-9 lllb-31
M-670 11-12 lllb-25 M-71 1 11-1 1 lllb-28 M-752 11-10 lllb-31
M-671 11-13 lllb-25 M-712 11-12 lllb-28 M-753 11-1 1 lllb-31
M-672 11-14 lllb-25 M-713 11-13 lllb-28 M-754 11-12 lllb-31
M-673 11-1 lllb-26 M-714 11-14 lllb-28 M-755 11-13 lllb-31
M-674 II-2 lllb-26 M-715 11-1 lllb-29 M-756 11-14 lllb-31
M-675 II-3 lllb-26 M-716 II-2 lllb-29 M-757 11-1 lllb-32
M-676 II-4 lllb-26 M-717 II-3 lllb-29 M-758 II-2 lllb-32
M-677 II-5 lllb-26 M-718 II-4 lllb-29 M-759 II-3 lllb-32
M-678 II-6 lllb-26 M-719 II-5 lllb-29 M-760 II-4 lllb-32
M-679 II-7 lllb-26 M-720 II-6 lllb-29 M-761 II-5 lllb-32
M-680 II-8 lllb-26 M-721 II-7 lllb-29 M-762 II-6 lllb-32
M-681 II-9 lllb-26 M-722 II-8 lllb-29 M-763 II-7 lllb-32
M-682 11-10 lllb-26 M-723 II-9 lllb-29 M-764 II-8 lllb-32
M-683 11-1 1 lllb-26 M-724 11-10 lllb-29 M-765 II-9 lllb-32
M-684 11-12 lllb-26 M-725 11-1 1 lllb-29 M-766 11-10 lllb-32
M-685 11-13 lllb-26 M-726 11-12 lllb-29 M-767 11-1 1 lllb-32
M-686 11-14 lllb-26 M-727 11-13 lllb-29 M-768 11-12 lllb-32
M-687 11-1 lllb-27 M-728 11-14 lllb-29 M-769 11-13 lllb-32
M-688 II-2 lllb-27 M-729 11-1 lllb-30 M-770 11-14 lllb-32
M-689 II-3 lllb-27 M-730 II-2 lllb-30 M-771 11-1 lllb-33
M-690 II-4 lllb-27 M-731 II-3 lllb-30 M-772 II-2 lllb-33
M-691 II-5 lllb-27 M-732 II-4 lllb-30 M-773 II-3 lllb-33
M-692 II-6 lllb-27 M-733 II-5 lllb-30 M-774 II-4 lllb-33
M-693 II-7 lllb-27 M-734 II-6 lllb-30 M-775 II-5 lllb-33
M-694 II-8 lllb-27 M-735 II-7 lllb-30 M-776 II-6 lllb-33
M-695 II-9 lllb-27 M-736 II-8 lllb-30 M-777 II-7 lllb-33
M-696 11-10 lllb-27 M-737 II-9 lllb-30 M-778 II-8 lllb-33
M-697 11-1 1 lllb-27 M-738 11-10 lllb-30 M-779 II-9 lllb-33
M-698 11-12 lllb-27 M-739 11-1 1 lllb-30 M-780 11-10 lllb-33
M-699 11-13 lllb-27 M-740 11-12 lllb-30 M-781 11-1 1 lllb-33
M-700 11-14 lllb-27 M-741 11-13 lllb-30 M-782 11-12 lllb-33
M-701 11-1 lllb-28 M-742 11-14 lllb-30 M-783 11-13 lllb-33
M-702 II-2 lllb-28 M-743 11-1 lllb-31 M-784 11-14 lllb-33
M-703 II-3 lllb-28 M-744 II-2 lllb-31 M-785 11-1 lllb-34
M-704 II-4 lllb-28 M-745 II-3 lllb-31 M-786 II-2 lllb-34 No. ll/lla III No. ll/lla III No. ll/lla III
M-787 II-3 lllb-34 M-828 lla-2 llla-1 M-869 lla-10 llla-4
M-788 II-4 lllb-34 M-829 lla-3 llla-1 M-870 lla-1 1 llla-4
M-789 II-5 lllb-34 M-830 lla-4 llla-1 M-871 lla-1 llla-5
M-790 II-6 lllb-34 M-831 lla-5 llla-1 M-872 lla-2 llla-5
M-791 II-7 lllb-34 M-832 lla-6 llla-1 M-873 lla-3 llla-5
M-792 II-8 lllb-34 M-833 lla-7 llla-1 M-874 lla-4 llla-5
M-793 II-9 lllb-34 M-834 lla-8 llla-1 M-875 lla-5 llla-5
M-794 11-10 lllb-34 M-835 lla-9 llla-1 M-876 lla-6 llla-5
M-795 11-1 1 lllb-34 M-836 lla-10 llla-1 M-877 lla-7 llla-5
M-796 11-12 lllb-34 M-837 lla-1 1 llla-1 M-878 lla-8 llla-5
M-797 11-13 lllb-34 M-838 lla-1 llla-2 M-879 lla-9 llla-5
M-798 11-14 lllb-34 M-839 lla-2 llla-2 M-880 lla-10 llla-5
M-799 11-1 lllb-35 M-840 lla-3 llla-2 M-881 lla-1 1 llla-5
M-800 II-2 lllb-35 M-841 lla-4 llla-2 M-882 lla-1 llla-6
M-801 II-3 lllb-35 M-842 lla-5 llla-2 M-883 lla-2 llla-6
M-802 II-4 lllb-35 M-843 lla-6 llla-2 M-884 lla-3 llla-6
M-803 II-5 lllb-35 M-844 lla-7 llla-2 M-885 lla-4 llla-6
M-804 II-6 lllb-35 M-845 lla-8 llla-2 M-886 lla-5 llla-6
M-805 II-7 lllb-35 M-846 lla-9 llla-2 M-887 lla-6 llla-6
M-806 II-8 lllb-35 M-847 lla-10 llla-2 M-888 lla-7 llla-6
M-807 II-9 lllb-35 M-848 lla-1 1 llla-2 M-889 lla-8 llla-6
M-808 11-10 lllb-35 M-849 lla-1 llla-3 M-890 lla-9 llla-6
M-809 11-1 1 lllb-35 M-850 lla-2 llla-3 M-891 lla-10 llla-6
M-810 11-12 lllb-35 M-851 lla-3 llla-3 M-892 lla-1 1 llla-6
M-81 1 11-13 lllb-35 M-852 lla-4 llla-3 M-893 lla-1 llla-7
M-812 11-14 lllb-35 M-853 lla-5 llla-3 M-894 lla-2 llla-7
M-813 11-1 lllb-36 M-854 lla-6 llla-3 M-895 lla-3 llla-7
M-814 II-2 lllb-36 M-855 lla-7 llla-3 M-896 lla-4 llla-7
M-815 II-3 lllb-36 M-856 lla-8 llla-3 M-897 lla-5 llla-7
M-816 II-4 lllb-36 M-857 lla-9 llla-3 M-898 lla-6 llla-7
M-817 II-5 lllb-36 M-858 lla-10 llla-3 M-899 lla-7 llla-7
M-818 II-6 lllb-36 M-859 lla-1 1 llla-3 M-900 lla-8 llla-7
M-819 II-7 lllb-36 M-860 lla-1 llla-4 M-901 lla-9 llla-7
M-820 II-8 lllb-36 M-861 lla-2 llla-4 M-902 lla-10 llla-7
M-821 II-9 lllb-36 M-862 lla-3 llla-4 M-903 lla-1 1 llla-7
M-822 11-10 lllb-36 M-863 lla-4 llla-4 M-904 lla-1 llla-8
M-823 11-1 1 lllb-36 M-864 lla-5 llla-4 M-905 lla-2 llla-8
M-824 11-12 lllb-36 M-865 lla-6 llla-4 M-906 lla-3 llla-8
M-825 11-13 lllb-36 M-866 lla-7 llla-4 M-907 lla-4 llla-8
M-826 11-14 lllb-36 M-867 lla-8 llla-4 M-908 lla-5 llla-8
M-827 lla-1 llla-1 M-868 lla-9 llla-4 M-909 lla-6 llla-8 No. ll/lla III No. ll/lla III No. ll/lla III
M-910 lla-7 llla-8 M-951 lla-4 llla-12 M-992 lla-1 llla-16
M-91 1 lla-8 llla-8 M-952 lla-5 llla-12 M-993 lla-2 llla-16
M-912 lla-9 llla-8 M-953 lla-6 llla-12 M-994 lla-3 llla-16
M-913 lla-10 llla-8 M-954 lla-7 llla-12 M-995 lla-4 llla-16
M-914 lla-1 1 llla-8 M-955 lla-8 llla-12 M-996 lla-5 llla-16
M-915 lla-1 llla-9 M-956 lla-9 llla-12 M-997 lla-6 llla-16
M-916 lla-2 llla-9 M-957 lla-10 llla-12 M-998 lla-7 llla-16
M-917 lla-3 llla-9 M-958 lla-1 1 llla-12 M-999 lla-8 llla-16
M-918 lla-4 llla-9 M-959 lla-1 3 M-1000 lla-9 llla-16
M-919 lla-5 llla-9 M-960 lla-2 llla-13 M-1001 lla-10 llla-16
M-920 lla-6 llla-9 M-961 lla-3 llla-13 M-1002 lla-1 1 llla-16
M-921 lla-7 llla-9 M-962 lla-4 llla-13 M-1003 lla-1 llla-17
M-922 lla-8 llla-9 M-963 lla-5 llla-13 M-1004 lla-2 llla-17
M-923 lla-9 llla-9 M-964 lla-6 llla-13 M-1005 lla-3 llla-17
M-924 lla-10 llla-9 M-965 lla-7 llla-13 M-1006 lla-4 llla-17
M-925 lla-1 1 llla-9 M-966 lla-8 llla-13 M-1007 lla-5 llla-17
M-926 lla-1 llla-10 M-967 lla-9 llla-13 M-1008 lla-6 llla-17
M-927 lla-2 llla-10 M-968 lla-10 llla-13 M-1009 lla-7 llla-17
M-928 lla-3 llla-10 M-969 lla-1 1 llla-13 M-1010 lla-8 llla-17
M-929 lla-4 llla-10 M-970 lla-1 llla-14 M-101 1 lla-9 llla-17
M-930 lla-5 llla-10 M-971 lla-2 llla-14 M-1012 lla-10 llla-17
M-931 lla-6 llla-10 M-972 lla-3 llla-14 M-1013 lla-1 1 llla-17
M-932 lla-7 llla-10 M-973 lla-4 llla-14 M-1014 lla-1 llla-18
M-933 lla-8 llla-10 M-974 lla-5 llla-14 M-1015 lla-2 llla-18
M-934 lla-9 llla-10 M-975 lla-6 llla-14 M-1016 lla-3 llla-18
M-935 lla-10 llla-10 M-976 lla-7 llla-14 M-1017 lla-4 llla-18
M-936 lla-1 1 llla-10 M-977 lla-8 llla-14 M-1018 lla-5 llla-18
M-937 lla-1 llla-1 1 M-978 lla-9 llla-14 M-1019 lla-6 llla-18
M-938 lla-2 llla-1 1 M-979 lla-10 llla-14 M-1020 lla-7 llla-18
M-939 lla-3 llla-1 1 M-980 lla-1 1 llla-14 M-1021 lla-8 llla-18
M-940 lla-4 llla-1 1 M-981 lla-1 llla- 5 M-1022 lla-9 llla-18
M-941 lla-5 llla-1 1 M-982 lla-2 llla-15 M-1023 lla-10 llla-18
M-942 lla-6 llla-1 1 M-983 lla-3 llla-15 M-1024 lla-1 1 llla-18
M-943 lla-7 llla-1 1 M-984 lla-4 llla-15 M-1025 lla-1 llla-19
M-944 lla-8 llla-1 1 M-985 lla-5 llla-15 M-1026 lla-2 llla-19
M-945 lla-9 llla-1 1 M-986 lla-6 llla-15 M-1027 lla-3 llla-19
M-946 lla-10 llla-1 1 M-987 lla-7 llla-15 M-1028 lla-4 llla-19
M-947 lla-1 1 llla-1 1 M-988 lla-8 llla-15 M-1029 lla-5 llla-19
M-948 lla-1 llla-12 M-989 lla-9 llla-15 M-1030 lla-6 llla-19
M-949 lla-2 llla-12 M-990 lla-10 llla-15 M-1031 lla-7 llla-19
M-950 lla-3 llla-12 M-991 lla-1 1 llla-15 M-1032 lla-8 llla-19 No. ll/lla III No. ll/lla III No. ll/lla III
M-1033 lla-9 llla-19 M-1074 lla-6 lllb-1 M-1115 lla-3 lllb-5
M-1034 lla-10 llla-19 M-1075 lla-7 lllb-1 M-1116 lla-4 lllb-5
M-1035 lla-11 llla-19 M-1076 lla-8 lllb-1 M-1117 lla-5 lllb-5
M-1036 lla-1 llla-20 M-1077 lla-9 lllb-1 M-1118 lla-6 lllb-5
M-1037 lla-2 llla-20 M-1078 lla-10 lllb-1 M-1119 lla-7 lllb-5
M-1038 lla-3 llla-20 M-1079 lla-11 lllb-1 M-1120 lla-8 lllb-5
M-1039 lla-4 llla-20 M-1080 lla-1 lllb-2 M-1121 lla-9 lllb-5
M-1040 lla-5 llla-20 M-1081 lla-2 lllb-2 M-1122 lla-10 lllb-5
M-1041 lla-6 llla-20 M-1082 lla-3 lllb-2 M-1123 lla-11 lllb-5
M-1042 lla-7 llla-20 M-1083 lla-4 lllb-2 M-1124 lla-1 lllb-6
M-1043 lla-8 llla-20 M-1084 lla-5 lllb-2 M-1125 lla-2 lllb-6
M-1044 lla-9 llla-20 M-1085 lla-6 lllb-2 M-1126 lla-3 lllb-6
M-1045 lla-10 llla-20 M-1086 lla-7 lllb-2 M-1127 lla-4 lllb-6
M-1046 lla-11 llla-20 M-1087 lla-8 lllb-2 M-1128 lla-5 lllb-6
M-1047 lla-1 llla-21 M-1088 lla-9 lllb-2 M-1129 lla-6 lllb-6
M-1048 lla-2 llla-21 M-1089 lla-10 lllb-2 M-1130 lla-7 lllb-6
M-1049 lla-3 llla-21 M-1090 lla-11 lllb-2 M-1131 lla-8 lllb-6
M-1050 lla-4 llla-21 M-1091 lla-1 lllb-3 M-1132 lla-9 lllb-6
M-1051 lla-5 llla-21 M-1092 lla-2 lllb-3 M-1133 lla-10 lllb-6
M-1052 lla-6 llla-21 M-1093 lla-3 lllb-3 M-1134 lla-11 lllb-6
M-1053 lla-7 llla-21 M-1094 lla-4 lllb-3 M-1135 lla-1 lllb-7
M-1054 lla-8 llla-21 M-1095 lla-5 lllb-3 M-1136 lla-2 lllb-7
M-1055 lla-9 llla-21 M-1096 lla-6 lllb-3 M-1137 lla-3 lllb-7
M-1056 lla-10 llla-21 M-1097 lla-7 lllb-3 M-1138 lla-4 lllb-7
M-1057 lla-11 llla-21 M-1098 lla-8 lllb-3 M-1139 lla-5 lllb-7
M-1058 lla-1 llla-22 M-1099 lla-9 lllb-3 M-1140 lla-6 lllb-7
M-1059 lla-2 llla-22 M-1100 lla-10 lllb-3 M-1141 lla-7 lllb-7
M-1060 lla-3 llla-22 M-1101 lla-11 lllb-3 M-1142 lla-8 lllb-7
M-1061 lla-4 llla-22 M-1102 lla-1 lllb-4 M-1143 lla-9 lllb-7
M-1062 lla-5 llla-22 M-1103 lla-2 lllb-4 M-1144 lla-10 lllb-7
M-1063 lla-6 llla-22 M-1104 lla-3 lllb-4 M-1145 lla-11 lllb-7
M-1064 lla-7 llla-22 M-1105 lla-4 lllb-4 M-1146 lla-1 lllb-8
M-1065 lla-8 llla-22 M-1106 lla-5 lllb-4 M-1147 lla-2 lllb-8
M-1066 lla-9 llla-22 M-1107 lla-6 lllb-4 M-1148 lla-3 lllb-8
M-1067 lla-10 llla-22 M-1108 lla-7 lllb-4 M-1149 lla-4 lllb-8
M-1068 lla-11 llla-22 M-1109 lla-8 lllb-4 M-1150 lla-5 lllb-8
M-1069 lla-1 lllb-1 M-1110 lla-9 lllb-4 M-1151 lla-6 lllb-8
M-1070 lla-2 lllb-1 M-1111 lla-10 lllb-4 M-1152 lla-7 lllb-8
M-1071 lla-3 lllb-1 M-1112 lla-11 lllb-4 M-1153 lla-8 lllb-8
M-1072 lla-4 lllb-1 M-1113 lla-1 lllb-5 M-1154 lla-9 lllb-8
M-1073 lla-5 lllb-1 M-1114 lla-2 lllb-5 M-1155 lla-10 lllb-8 No. ll/lla III No. ll/lla III No. ll/lla III
M-1156 lla-11 lllb-8 M-1197 lla-8 lllb-12 M-1238 lla-5 lllb-16
M-1157 lla-1 lllb-9 M-1198 lla-9 lllb-12 M-1239 lla-6 lllb-16
M-1158 lla-2 lllb-9 M-1199 lla-10 lllb-12 M-1240 lla-7 lllb-16
M-1159 lla-3 lllb-9 M-1200 lla-11 lllb-12 M-1241 lla-8 lllb-16
M-1160 lla-4 lllb-9 M-1201 lla-1 lllb-13 M-1242 lla-9 lllb-16
M-1161 lla-5 lllb-9 M-1202 lla-2 lllb-13 M-1243 lla-10 lllb-16
M-1162 lla-6 lllb-9 M-1203 lla-3 lllb-13 M-1244 lla-11 lllb-16
M-1163 lla-7 lllb-9 M-1204 lla-4 lllb-13 M-1245 lla-1 lllb-17
M-1164 lla-8 lllb-9 M-1205 lla-5 lllb-13 M-1246 lla-2 lllb-17
M-1165 lla-9 lllb-9 M-1206 lla-6 lllb-13 M-1247 lla-3 lllb-17
M-1166 lla-10 lllb-9 M-1207 lla-7 lllb-13 M-1248 lla-4 lllb-17
M-1167 lla-11 lllb-9 M-1208 lla-8 lllb-13 M-1249 lla-5 lllb-17
M-1168 lla-1 lllb-10 M-1209 lla-9 lllb-13 M-1250 lla-6 lllb-17
M-1169 lla-2 lllb-10 M-1210 lla-10 lllb-13 M-1251 lla-7 lllb-17
M-1170 lla-3 lllb-10 M-1211 lla-11 lllb-13 M-1252 lla-8 lllb-17
M-1171 lla-4 lllb-10 M-1212 lla-1 lllb-14 M-1253 lla-9 lllb-17
M-1172 lla-5 lllb-10 M-1213 lla-2 lllb-14 M-1254 lla-10 lllb-17
M-1173 lla-6 lllb-10 M-1214 lla-3 lllb-14 M-1255 lla-11 lllb-17
M-1174 lla-7 lllb-10 M-1215 lla-4 lllb-14 M-1256 lla-1 lllb-18
M-1175 lla-8 lllb-10 M-1216 lla-5 lllb-14 M-1257 lla-2 lllb-18
M-1176 lla-9 lllb-10 M-1217 lla-6 lllb-14 M-1258 lla-3 lllb-18
M-1177 lla-10 lllb-10 M-1218 lla-7 lllb-14 M-1259 lla-4 lllb-18
M-1178 lla-11 lllb-10 M-1219 lla-8 lllb-14 M-1260 lla-5 lllb-18
M-1179 lla-1 lllb-11 M-1220 lla-9 lllb-14 M-1261 lla-6 lllb-18
M-1180 lla-2 lllb-11 M-1221 lla-10 lllb-14 M-1262 lla-7 lllb-18
M-1181 lla-3 lllb-11 M-1222 lla-11 lllb-14 M-1263 lla-8 lllb-18
M-1182 lla-4 lllb-11 M-1223 lla-1 lllb-15 M-1264 lla-9 lllb-18
M-1183 lla-5 lllb-11 M-1224 lla-2 lllb-15 M-1265 lla-10 lllb-18
M-1184 lla-6 lllb-11 M-1225 lla-3 lllb-15 M-1266 lla-11 lllb-18
M-1185 lla-7 lllb-11 M-1226 lla-4 lllb-15 M-1267 lla-1 lllb-19
M-1186 lla-8 lllb-11 M-1227 lla-5 lllb-15 M-1268 lla-2 lllb-19
M-1187 lla-9 lllb-11 M-1228 lla-6 lllb-15 M-1269 lla-3 lllb-19
M-1188 lla-10 lllb-11 M-1229 lla-7 lllb-15 M-1270 lla-4 lllb-19
M-1189 lla-11 lllb-11 M-1230 lla-8 lllb-15 M-1271 lla-5 lllb-19
M-1190 lla-1 lllb-12 M-1231 lla-9 lllb-15 M-1272 lla-6 lllb-19
M-1191 lla-2 lllb-12 M-1232 lla-10 lllb-15 M-1273 lla-7 lllb-19
M-1192 lla-3 lllb-12 M-1233 lla-11 lllb-15 M-1274 lla-8 lllb-19
M-1193 lla-4 lllb-12 M-1234 lla-1 lllb-16 M-1275 lla-9 lllb-19
M-1194 lla-5 lllb-12 M-1235 lla-2 lllb-16 M-1276 lla-10 lllb-19
M-1195 lla-6 lllb-12 M-1236 lla-3 lllb-16 M-1277 lla-11 lllb-19
M-1196 lla-7 lllb-12 M-1237 lla-4 lllb-16 M-1278 lla-1 lllb-20 No. ll/lla III No. ll/lla III No. ll/lla III
M-1279 lla-2 lllb-20 M-1320 lla-10 lllb-23 M-1361 lla-7 lllb-27
M-1280 lla-3 lllb-20 M-1321 lla-1 1 lllb-23 M-1362 lla-8 lllb-27
M-1281 lla-4 lllb-20 M-1322 lla-1 lllb-24 M-1363 lla-9 lllb-27
M-1282 lla-5 lllb-20 M-1323 lla-2 lllb-24 M-1364 lla-10 lllb-27
M-1283 lla-6 lllb-20 M-1324 lla-3 lllb-24 M-1365 lla-1 1 lllb-27
M-1284 lla-7 lllb-20 M-1325 lla-4 lllb-24 M-1366 lla-1 lllb-28
M-1285 lla-8 lllb-20 M-1326 lla-5 lllb-24 M-1367 lla-2 lllb-28
M-1286 lla-9 lllb-20 M-1327 lla-6 lllb-24 M-1368 lla-3 lllb-28
M-1287 lla-10 lllb-20 M-1328 lla-7 lllb-24 M-1369 lla-4 lllb-28
M-1288 lla-1 1 lllb-20 M-1329 lla-8 lllb-24 M-1370 lla-5 lllb-28
M-1289 lla-1 lllb-21 M-1330 lla-9 lllb-24 M-1371 lla-6 lllb-28
M-1290 lla-2 lllb-21 M-1331 lla-10 lllb-24 M-1372 lla-7 lllb-28
M-1291 lla-3 lllb-21 M-1332 lla-1 1 lllb-24 M-1373 lla-8 lllb-28
M-1292 lla-4 lllb-21 M-1333 lla-1 lllb-25 M-1374 lla-9 lllb-28
M-1293 lla-5 lllb-21 M-1334 lla-2 lllb-25 M-1375 lla-10 lllb-28
M-1294 lla-6 lllb-21 M-1335 lla-3 lllb-25 M-1376 lla-1 1 lllb-28
M-1295 lla-7 lllb-21 M-1336 lla-4 lllb-25 M-1377 lla-1 lllb-29
M-1296 lla-8 lllb-21 M-1337 lla-5 lllb-25 M-1378 lla-2 lllb-29
M-1297 lla-9 lllb-21 M-1338 lla-6 lllb-25 M-1379 lla-3 lllb-29
M-1298 lla-10 lllb-21 M-1339 lla-7 lllb-25 M-1380 lla-4 lllb-29
M-1299 lla-1 1 lllb-21 M-1340 lla-8 lllb-25 M-1381 lla-5 lllb-29
M-1300 lla-1 lllb-22 M-1341 lla-9 lllb-25 M-1382 lla-6 lllb-29
M-1301 lla-2 lllb-22 M-1342 lla-10 lllb-25 M-1383 lla-7 lllb-29
M-1302 lla-3 lllb-22 M-1343 lla-1 1 lllb-25 M-1384 lla-8 lllb-29
M-1303 lla-4 lllb-22 M-1344 lla-1 lllb-26 M-1385 lla-9 lllb-29
M-1304 lla-5 lllb-22 M-1345 lla-2 lllb-26 M-1386 lla-10 lllb-29
M-1305 lla-6 lllb-22 M-1346 lla-3 lllb-26 M-1387 lla-1 1 lllb-29
M-1306 lla-7 lllb-22 M-1347 lla-4 lllb-26 M-1388 lla-1 lllb-30
M-1307 lla-8 lllb-22 M-1348 lla-5 lllb-26 M-1389 lla-2 lllb-30
M-1308 lla-9 lllb-22 M-1349 lla-6 lllb-26 M-1390 lla-3 lllb-30
M-1309 lla-10 lllb-22 M-1350 lla-7 lllb-26 M-1391 lla-4 lllb-30
M-1310 lla-1 1 lllb-22 M-1351 lla-8 lllb-26 M-1392 lla-5 lllb-30
M-131 1 lla-1 lllb-23 M-1352 lla-9 lllb-26 M-1393 lla-6 lllb-30
M-1312 lla-2 lllb-23 M-1353 lla-10 lllb-26 M-1394 lla-7 lllb-30
M-1313 lla-3 lllb-23 M-1354 lla-1 1 lllb-26 M-1395 lla-8 lllb-30
M-1314 lla-4 lllb-23 M-1355 lla-1 lllb-27 M-1396 lla-9 lllb-30
M-1315 lla-5 lllb-23 M-1356 lla-2 lllb-27 M-1397 lla-10 lllb-30
M-1316 lla-6 lllb-23 M-1357 lla-3 lllb-27 M-1398 lla-1 1 lllb-30
M-1317 lla-7 lllb-23 M-1358 lla-4 lllb-27 M-1399 lla-1 lllb-31
M-1318 lla-8 lllb-23 M-1359 lla-5 lllb-27 M-1400 lla-2 lllb-31
M-1319 lla-9 lllb-23 M-1360 lla-6 lllb-27 M-1401 lla-3 lllb-31 No. ll/lla III No. ll/lla III No. ll/lla III
M-1402 lla-4 lllb-31 M-1423 lla-3 lllb-33 M-1444 lla-2 lllb-35
M-1403 lla-5 lllb-31 M-1424 lla-4 lllb-33 M-1445 lla-3 lllb-35
M-1404 lla-6 lllb-31 M-1425 lla-5 lllb-33 M-1446 lla-4 lllb-35
M-1405 lla-7 lllb-31 M-1426 lla-6 lllb-33 M-1447 lla-5 lllb-35
M-1406 lla-8 lllb-31 M-1427 lla-7 lllb-33 M-1448 lla-6 lllb-35
M-1407 lla-9 lllb-31 M-1428 lla-8 lllb-33 M-1449 lla-7 lllb-35
M-1408 lla-10 lllb-31 M-1429 lla-9 lllb-33 M-1450 lla-8 lllb-35
M-1409 lla-1 1 lllb-31 M-1430 lla-10 lllb-33 M-1451 lla-9 lllb-35
M-1410 lla-1 lllb-32 M-1431 lla-1 1 lllb-33 M-1452 lla-10 lllb-35
M-141 1 lla-2 lllb-32 M-1432 lla-1 lllb-34 M-1453 lla-1 1 lllb-35
M-1412 lla-3 lllb-32 M-1433 lla-2 lllb-34 M-1454 lla-1 lllb-36
M-1413 lla-4 lllb-32 M-1434 lla-3 lllb-34 M-1455 lla-2 lllb-36
M-1414 lla-5 lllb-32 M-1435 lla-4 lllb-34 M-1456 lla-3 lllb-36
M-1415 lla-6 lllb-32 M-1436 lla-5 lllb-34 M-1457 lla-4 lllb-36
M-1416 lla-7 lllb-32 M-1437 lla-6 lllb-34 M-1458 lla-5 lllb-36
M-1417 lla-8 lllb-32 M-1438 lla-7 lllb-34 M-1459 lla-6 lllb-36
M-1418 lla-9 lllb-32 M-1439 lla-8 lllb-34 M-1460 lla-7 lllb-36
M-1419 lla-10 lllb-32 M-1440 lla-9 lllb-34 M-1461 lla-8 lllb-36
M-1420 lla-1 1 lllb-32 M-1441 lla-10 lllb-34 M-1462 lla-9 lllb-36
M-1421 lla-1 lllb-33 M-1442 lla-1 1 lllb-34 M-1463 lla-10 lllb-36
M-1422 lla-2 lllb-33 M-1443 lla-1 lllb-35 M-1464 lla-1 1 lllb-36
In a further embodiment, the present invention relates to agriculatural compositions comprising a mixture of the invention, in particular any one of the mixtures A-1 to A-252 or B-1 to B-198, or I-1 -M-1 to I-1-M-1464, I-2-M-1 to I-2-M-1464, I-3-M-1 to I-3-M-1464, I-4-M-1 to I-4-M-1464, I-5- M-1 to I-5-M-1464, I-6-M-1 to I-6-M-1464, I-7-M-1 to I-7-M-1464, I-8-M-1 to I-8-M-1464, I-9-M-1 to I-9-M-1464, I-10-M-1 to I-10-M-1464, I-1 1-M-1 to 1-1 1 -M-1464, I-12-M-1 to I-12-M-1464, 1-13- M-1 to I-13-M-1464, I-14-M-1 to I-14-M-1464, I-15-M-1 to I-15-M-1464, I-16-M-1 to I-16-M-1464, I-17-M-1 to I-17-M-1464, or I-18-M-1 to I-18-M-1464.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the
agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
Preferences regarding suitable formulations and auxiliaries, which may be present in such agricultural compositions are defined below.
According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
When living microorganisms, such as microbial pesticides from groups L1 ), L3) and L5), form part of such kit, it must be taken care that choice and amounts of the components (e. g.
chemical pesticides) and of the further auxiliaries should not influence the viability of the microbial pesticides in the composition mixed by the user. Especially for bactericides and solvents, compatibility with the respective microbial pesticide has to be taken into account.
Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1 ) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
In a further embodiment, the present invention relates to a seed treatment composition comprising an auxiliary and a mixture of the invention, preferably any one of the mixtures A-1 to A-252 or B-1 to B-198, or I-1 -M-1 to I-1-M-1464, I-2-M-1 to I-2-M-1464, I-3-M-1 to I-3-M-1464, I- 4-M-1 to I-4-M-1464, I-5-M-1 to I-5-M-1464, I-6-M-1 to I-6-M-1464, I-7-M-1 to I-7-M-1464, I-8-M- 1 to I-8-M-1464, I-9-M-1 to I-9-M-1464, I-10-M-1 to I-10-M-1464, I-1 1-M-1 to 1-1 1-M-1464, 1-12- M-1 to I-12-M-1464, I-13-M-1 to I-13-M-1464, I-14-M-1 to I-14-M-1464, I-15-M-1 to I-15-M-1464, I-16-M-1 to I-16-M-1464, I-17-M-1 to I-17-M-1464, or I-18-M-1 to I-18-M-1464, wherein the auxiliary is preferably selected from the group consisting of surfactants, antifreezing agents, binders, and pigments, and is particularly preferably a surfactant or a binder.
In a preferred embodiment, the seed treatment composition is in the form of a flowable concentrate FS, a solution LS, a powder for dry treatment DS, a water dispersible powder for slurry treatment WS, a water-soluble powder SS, an emulsion ES or EC, or a gel formulation, and is preferably in the form of a flowable concentrate.
Further preferences regarding seed treatment compositions of the invention are defined below.
In one embodiment, the present invention relates to the use of a mixture of the invention, in particular a mixture selected from the mixtures A-1 to A-252 or B-1 to B-198, or 1-1 -M-1 to 1-1 -M- 1464, I-2-M-1 to I-2-M-1464, I-3-M-1 to I-3-M-1464, I-4-M-1 to I-4-M-1464, I-5-M-1 to I-5-M- 1464, I-6-M-1 to I-6-M-1464, I-7-M-1 to I-7-M-1464, I-8-M-1 to I-8-M-1464, I-9-M-1 to I-9-M- 1464, I-10-M-1 to I-10-M-1464, I-1 1-M-1 to 1-1 1 -M-1464, I-12-M-1 to I-12-M-1464, I-13-M-1 to I- 13-M-1464, I-14-M-1 to I-14-M-1464, I-15-M-1 to I-15-M-1464, I-16-M-1 to I-16-M-1464, I-17-M- 1 to I-17-M-1464, or I-18-M-1 to I-18-M-1464, or a seed treatment composition as defined above, for protecting a plant, plant propagation material, or soil or water, in which the plants are growing, against the attack or infestation by invertebrate pests.
In another embodiment, the present invention relates to a method for controlling invertebrate pests, which method comprises contacting the plant or the plant propagation material or the soil; the pests or their food supply, habitat or breeding grounds, with a pesticidally effective amount of a mixture of the invention, in particular a mixture selected from the mixtures A-1 to A-108 or B-1 to B-108, or a seed treatment composition as defined above.
Preferences regarding plants, pests and application methods are defined below. In one embodiment, the present invention relates to seeds comprising the mixture of the invention, in particular a mixture selected from the mixtures A-1 to A-252 or B-1 to B-198, or 1-1- M-1 to I-1-M-1464, I-2-M-1 to I-2-M-1464, I-3-M-1 to I-3-M-1464, I-4-M-1 to I-4-M-1464, I-5-M-1 to I-5-M-1464, I-6-M-1 to I-6-M-1464, I-7-M-1 to I-7-M-1464, I-8-M-1 to I-8-M-1464, I-9-M-1 to I- 9-M-1464, I-10-M-1 to I-10-M-1464, I-1 1 -M-1 to 1-1 1 -M-1464, I-12-M-1 to I-12-M-1464, I-13-M-1 to I-13-M-1464, I-14-M-1 to I-14-M-1464, I-15-M-1 to I-15-M-1464, I-16-M-1 to I-16-M-1464, I- 17-M-1 to I-17-M-1464, or I-18-M-1 to I-18-M-1464, or a seed treatment composition as defined above in an amount of from 0.01 g to 10000 g per 100 kg of seeds.
It is noted that the amount per 100 kg seeds is based on the weight of the pesticidal mixture irrespective of whether it is referred to the mixture as such or the seed treatment composition thereof.
Preferred seeds are seeds selected from wheat, maize, barley, oat, rye, rice, soybean, cotton, sugarbeet, rapeseed, and potato. With regard to all the mixtures of the invention as defined herein, the following embodiments are additionally preferred.
The mixtures of the present invention may be combined and applied in agriculture in mixture with other active ingredients, for example with other pesticides, insecticides, nematicides, fungicides, herbicides, safeners, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators.
These additional ingredients may be used sequentially or in combination with the mixtures of the invention, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a mixture of this invention either before or after being treated with other active ingredients.
The invention also relates to agrochemical compositions comprising an auxiliary and at least one mixture of the present invention.
An agrochemical composition comprises a pesticidally effective amount of a mixture of the present invention. The term "pesticidally effective amount" is defined below.
The mixtures of the present invention 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 such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Mono-graph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. Examples for 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, tackifi- ers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo^hexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch;
fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth- oxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Exam- pies of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are homo- or copolymers of
vinylpyrrolidone, vinylalcohols, or vinylacetate. Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the mixtures of the present invention on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of the mixture according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of the mixture according to the invention and 1-10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of the mixture according to the invention and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100 wt% water- insoluble organic solvent (e.g. aromatic hydrocarbon). Dilution with water gives an emulsion. iv) Emulsions (EW, EO, ES)
5-40 wt% of the mixture according to the invention and 1-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into up to 100 wt% water by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion. v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of the mixture according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1-2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of the mixture according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of the mixture according to the invention are ground in a rotor-stator mill with ad- dition of 1-5 wt% dispersants (e.g. sodium lignosulfonate), 1-3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of the mixture according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. car- boxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
ix) Microemulsion (ME)
5-20 wt% of the mixture according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of the mixture according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g.
methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of the mixture according to the invention, 0-40 wt% water insolu-ble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylme- thene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of a polyurea microcapsule. The monomers amount to 1-10 wt%. The wt% relate to the total CS composition.
xi) Dustable powders (DP, DS)
1 -10 wt% of a the mixture according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
xii) Granules (GR, FG)
0.5-30 wt% of the mixture according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.
xiii) Ultra-low volume liquids (UL)
1 -50 wt% of the mixture according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
The compositions types i) to xi) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% colorants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably be- tween 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% (according to NMR spectrum).
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions cormprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
The user applies the composition according to the invention usually from a predosage de-vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, individual components of the composition according to the in- vention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e.g. components comprising mixtures of the present invention, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising mixtures of the present invention, can be applied jointly (e.g. after tank mix) or consecutively. The mixtures of the present invention are suitable for use in protecting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the present invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, such as 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 present invention.
The mixtures of the present invention are also suitable for use in combating or controlling animal pests. Therefore, the present 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, such as 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 present invention.
The mixtures of the present invention are effective through both contact and ingestion.
Furthermore, the mixtures of the present invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.
The mixtures of the present invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the mixtures of the present invention can be applied together with a mixing partner as defined above or in form of compositions comprising said mixtures as defined above. The components of said mixture can be applied
simultaneously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture "in situ" on the desired location, e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
The application can be carried out both before and after the infestation of the crops, plants, plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.
Suitable application methods include inter alia soil treatment, seed treatment, in furrow application, and foliar application. Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting. In furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pesticidally active mixture to the furrow, and closing the furrow. Foliar application refers to the application of the pesticidally active mixture to plant foliage, e.g. through spray equipment. For foliar applications, it can be advantageous to modify the behavior of the pests by use of pheromones in combination with the mixtures of the present invention. Suitable pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as http://www.pherobase.com.
As used herein, the term "contacting" includes both direct contact (applying the
mixtures/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the mixtures/compositions to the locus, i.e. habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).
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. Insects, which are of particular relevance for crops, are typically referred to as crop insect pests.
The term "crop" refers to both, growing and harvested crops.
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, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, nectarines, almonds, cherries, papayas, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as beans, lentils, peas, alfalfa or soybeans; oil plants, such as rapeseed (oilseed rape), turnip rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, pumpkins, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as eggplant, spinach, lettuce (e.g. iceberg lettuce), chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers (e.g. carnation, petunias,
geranium/pelargoniums, pansies and impatiens), shrubs, broad-leaved trees (e.g. poplar) or evergreens, e.g. conifers; eucalyptus; turf; lawn; grass such as grass for animal feed or ornamental uses. 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, such as cucumbers, tomatoes, beans or squashes.
The term "plant" is to be understood as including wild type plants and plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof.
Plants, which have been modified by mutagenesis or genetic engineering, and are of particular commercial importance, include alfalfa, rapeseed (e.g. oilseed rape), bean, carnation, chicory, cotton, eggplant, eucalyptus, flax, lentil, maize, melon, papaya, petunia, plum, poplar, potato, rice, soybean, squash, sugar beet, sugarcane, sunflower, sweet pepper, tobacco, tomato, and cereals (e.g. wheat), in particular maize, soybean, cotton, wheat, and rice. In plants, which have been modified by mutagenesis or genetic engineering, one or more genes have been mutagenized or integrated into the genetic material of the plant. The one or more mutagenized or integrated genes are preferably selected from pat, epsps, crylAb, bar, cry1 Fa2, crylAc, cry34Ab1 , cry35AB1 , cry3A, cryF, cry1 F, mcry3a, cry2Ab2, cry3Bb1 , cry1A.105, dfr, barnase, vip3Aa20, barstar, als, bxn, bp40, asnl , and ppo5. The mutagenesis or integration of the one or more genes is performed in order to improve certain properties of the plant. Such properties, also known as traits, include abiotic stress tolerance, altered growth/yield, disease resistance, herbicide tolerance, insect resistance, modified product quality, and pollination control. Of these properties, herbicide tolerance, e.g. imidazolinone tolerance, glyphosate tolerance, or glufosinate tolerance, is of particular importance. Several plants have been rendered tolerant to herbicides by mutagenesis, for example Clearfield® oilseed rape being tolerant to
imidazolinones, e.g. imazamox. Alternatively, genetic engineering methods have been used to render plants, such as soybean, cotton, corn, beets and oil seed rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate). Furthermore, insect resistance is of importance, in particular lepidopteran insect resistance and coleopteran insect resistance. Insect resistance is typically achieved by modifying plants by integrating cry and/or vip genes, which were isolated from Bacillus thuringiensis (Bt), and code for the respective Bt toxins. Genetically modified plants with insect resistance are commercially available under trade names including WideStrike®, Bollgard®, Agrisure®, Herculex®, YieldGard®, Genuity®, and Intacta®. Plants may be modified by mutagenesis or genetic engineering either in terms of one property (singular traits) or in terms of a combination of properties (stacked traits). Stacked traits, e.g. the combination of herbicide tolerance and insect resistance, are of increasing importance. In general, all relevant modified plants in connection with singular or stacked traits as well as detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations "International Service for the Acquisition of Agri-biotech Applications (ISAAA)" (http://www.isaaa.org/gmapprovaldatabase) and "Center for Environmental Risk Assessment (CERA)" (http://cera-gmc.org/GMCropDatabase).
The term "plant propagation material" refers to all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection mixture either at or before planting or transplanting.
The term "seed" embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like, and means in a preferred embodiment true seeds.
In general, "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
mixtures/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
In the case of soil treatment, in furrow application or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 20 g per 100 m2.
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, more desirably from 10 g to 50 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare, or 40 to 50 g per hectare.
The mixtures of the present invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling's roots and shoots against soil pests and foliar insects. The present invention therefore also relates to a method for the protection of seeds from insects, in particular from soil insects, and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising treating the seeds before sowing and/or after pregermination with a mixture of the present invention. The protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling's shoots from piercing and sucking insects, chewing insects and nematodes.
The term "seed treatment" comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods. Preferably, the seed treatment application of the active mixture is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
The present invention also comprises seeds coated with or containing the active mixture. 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 for example seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example 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 such as potatoes, sugar cane, tobacco, grapes, petunias,
geranium/pelargoniums, pansies and impatiens.
In addition, the active mixture 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. Such modified plants have been described in detail above.
Conventional seed treatment formulations include for example 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 antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Especially preferred FS formulations of the mixtures of the present 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 such as 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 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 mixture of the present invention, or an agriculturally useful salt thereof, as defined herein. The amount of the mixture of the present 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 such as lettuce the rate can be higher.
The mixtures of the present invention may also be used for improving the health of a plant. Therefore, the present invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the locus where the plant is growing or is to grow with an effective and non-phytotoxic amount of a mixture of the present invention.
As used herein "an effective and non-phytotoxic amount" means that the mixture is used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptom on the treated plant or on the plant grown from the treated propagule or treated soil. The terms "plant" and "plant propagation material" are defined above.
"Plant health" is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass and/or increased content of valuable ingredients), quality (for example improved content or composition of certain ingredients or shelf life), plant vigour (for example improved plant growth and/or greener leaves ("greening effect"), tolerance to abiotic (for example drought) and/or biotic stress (for example disease) and production efficiency (for example, harvesting efficiency, processability).
The above identified indicators for the health condition of a plant may be interdependent and may result from each other. Each indicator is defined in the art and can be determined by methods known to a skilled person.
The mixtures of the invention are also suitable for use against non-crop insect pests. For use against said non-crop pests, mixtures of the present invention can be used as bait composition, gel, general insect spray, aerosol, as ultra-low volume application and bed net (impregnated or surface applied). Furthermore, drenching and rodding methods can be used.
As used herein, the term "non-crop insect pest" refers to pests, which are particularly relevant for non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitos, crickets, or cockroaches.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature (e.g.
http://www.pherobase.com), and are known to those skilled in the art.
For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active mixture.
Formulations of the mixtures of the present invention as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active mixture, solvents, furthermore auxiliaries such as emulsifiers, perfume oils, if appropriate stabilizers, and, if required, propellants.
The oil spray formulations differ from the aerosol recipes in that no propellants are used.
For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
The mixtures of the present invention and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with mixtures of the present invention and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.
The mixtures of the present invention and its compositions can be used for protecting wooden materials such as trees, board fences, sleepers, frames, artistic artifacts, etc. and buildings, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
Customary application rates in the protection of materials are, for example, from 0.001 g to 2000 g or from 0.01 g to 1000 g of active mixture per m2 treated material, desirably from 0.1 g to 50 g per m2.
Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.
The mixtures of the the present invention are especially suitable for efficiently combating animal pests such as arthropods, gastropods and nematodes including but not limited to:
insects from the order of Lepidoptera, for example Achroia grisella, Aden's spp. such as A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrot/s spp. such as 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 senator/a, Antheraea pernyi, Anti- carsia (=Thermesia) spp. such as A. gemmatalis; Apamea spp., Aproaerema modicella, Archips spp. such as A. argyrospila, A. fuscocupreanus, A. rosana, A. xyloseanus; Argyresthia conju- gella, Argyroploce spp., Argyrotaenia spp. such as 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. such as C. murinana, C. podana; Cactoblastis cactorum, Cadra cautella, Calingo braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C niponensis, C sasakii; Cephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. such as C Indicus, C suppressalis, C partellus; Choreutis pariana, Choristoneura spp. such as C con- flictana, C fumiferana, C longicellana, C murinana, C occidentalis, C rosaceana; Chryso- deixis (=Pseudoplusia) spp. such as C. eriosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cnapha/ocrocis medina/is, Cnephasia spp., Cochy/is hospes, Co/eophora spp., Co/ias eurytheme, Conopomorpha spp., Conotrache/us spp., Cop/tarsia spp., Corcyra cepha/onica, Crambus caliginosellus, Crambus teterrellus, Crocidosema (=Epinotia) aporema, Cydalima (=Diaphania) perspectalis, Cydia (=Carpocapsa) spp. such as C. pomo- nella, C latiferreana; Dalaca noctuides, Datana integerrima, Dasychira pinicola, Dendrolimus spp. such as D. pini, D. spectabilis, D. sibiricus; Desmia funeralis, Diaphania spp. such as D. nitidalis, D. hyalinata; Diatraea grandiose/la, Diatraea saccharalis, Diphthera festiva, Ear/as spp. such as E. insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) curia/is, Elasmo- palpus lignosellus, Eldana saccharina, Endopiza viteana, Ennomos subsignaria, Eoreuma loftini, Ephestia spp. such as E. cautella, E. elutella, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etie/ia spp., Eu/ia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Fe/tia spp. such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as G. funebrana, G molesta, G. inopinata; Halysidota spp., Harrisina americana, Hedylepta spp., Helicoverpa spp. such as H. armigera (=Heliothis armigera), H. zea (=Heliothis zea); Heliothis spp. such as H. assulta, H. subflexa, H. virescens; Hellula spp. such as 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 lyco- persicella, Lambdina fiscellaria fiscellaria, Lambdina fiscellaria lugubrosa, Lamprosema indica- ta, Laspeyresia molesta, Leguminivora glycinivorella, Lerodea eufala, Leucinodes orbonalis, Leucoma salicis, Leucoptera spp. such as L. coffeella, L. scitella; Leuminivora lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo (=Amyna axis), Lobes/a botrana, Lophocam pa spp., Loxagrotis albicosta, Loxostege spp. such as L. sticticalis, L. cereralis;
Lymantria spp. such as L. dispar, L. monacha; Lyonetia clerkella, Lyonetia prunifoliella, Mala- cosoma spp. such as M. americanum, M. californicum, M. constrictum, M. neustria; Mamestra spp. such as M. brassicae, M. configurata; Mamstra brassicae, Manduca spp. such as M. quin- quemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mods spp. such as M. lapites, M. repanda; Mods latipes, Monochroa fragariae, Mythimna separata, Nemapogon cloacella, Neoleucinodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes indicata, Omphisa anastomosalis, Operophtera brumata, Orgy/a pseudotsugata, Or/a spp., Orthaga thyr/sa/is, Ostr/n/a spp. such as O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paranthrene regalis, Paysandisia archon, Pectinophora spp. such as P. gossypiella; Peridroma saucia, Perileucoptera spp., such as P. coffeella; Phalera bucephala, Phryganidia californica, Phthorimaea spp. such as P. operculella; Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathy- pena scabra, Platynota spp. such as P. flavedana, P. idaeusalis, P. stultana; Platyptilia cardu- idactyla, Plebejus argus, Plodia interpunctella, Plusia spp, Plutella maculipennis, Plutella xylostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus /epigone, Pseudaletia spp. such as P. sequax, P. unipuncta; Pyrausta nubilalis, Rachiplusia nu, Richia albicosta, Rhizobius ventralis, Rhyacionia frustrana, Sabulodes aegrotata, Schizura concinna, Schoenobius spp., Schreckensteinia festaliella, Scirpophaga spp. such as S. incertulas, S. innotata; Scotia sege- tum, Sesamia spp. such as S. inferens, Seudyra subflava, Sitotroga cerealella, Sparganothis pilleriana, Spilonota lechriaspis, S. ocellana, Spodoptera (=Lamphygma) spp. such as S. erida- nia, S. exigua, S. frugiperda, S. latisfascia, S. littoralis, S. litura, S. omithogalli; Stigmella spp., Stomopteryx subsecivella, Strymon bazochii, Sylepta derogata, Synanthedon spp. such as S. exitiosa, Tec/a solanivora, Telehin ileus, Thaumatopoea pityocampa, Thaumatotibia (=Crypto- phlebia) leucotreta, Thaumetopoea pityocampa, Thecla spp., Theresimima ampelophaga, Thy- rinteina spp, Tildenia inconspicuella, Tinea spp. such as T. cloacella, T. pellionella; Tineola bisselliella, Tortrix spp. such as T. viridana; Trichophaga tapetzella, Trichoplusia spp. such as T. ni; Tuta (=Scrobipalpula) absoluta, Udea spp. such as U. rubigalis, U. rubigalis; Virachola spp., Yponomeuta padella, and Zeiraphera canadensis;
insects from the order of Coleoptera, for example Acalymma vittatum, Acanthoscehdes obtec- tus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphi- mallus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala corpu- lenta, Anomala rufocuprea, Anoplophora spp. such as A. glabripennis; Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apo- gonia spp., Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp., Aulaco- phora femora/is, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Callopis- tria floridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp. such as C. assimilis, C. napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp. such as C. vespertinus; Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryp- torhynchus lapathi, Ctenicera spp. such as C. destructor; Curculio spp., Cylindrocopturus spp., Cyclocephala spp., Dactyl/spa ba/yi, Dectes texanus, Dermestes spp., Diabrotica spp. such as 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. such as E. varivestis, E. vigin- tioctomaculata; Epitrix spp. such as E. hirtipennis, E. similaris; Eutheola humilis, Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Hete- ronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera spp. such as H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typogra- phus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp. such as L bilineata, L. melanopus; Leptinotarsa spp. such as L decemlineata;
Leptispa pygmaea, Limonius californicus, Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp. such as L. bruneus; Liogenys fuscus, Macrodactylus spp. such as M. subspi- nosus; Maladera matrida, Megaplatypus mutates, Megascelis spp., Melanotus communis, Meli- gethes spp. such as M. aeneus; Melolontha spp. such as M. hippocastani, M. melolontha; Meta- masius hemipterus, Microtheca spp., Migdolus spp. such as M. fryanus, Monochamus spp. such as 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. such as P. brassicae, P. cochleariae; Phoracantha recurva, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp. such as P. helleri; Phyllotreta spp. such as P. chrysocephala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Pop/ilia japonica, Premnotrypes spp., Psacothea hilaris, Psylliodes chrysocephala, Prostephanus truncates, Psylliodes spp., Ptinus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp. such as R. billineatus, R. ferrugineus, R. pa/marum, R. phoenicis, R. vulneratus; Saperda Candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. such as S. granaria, S. oryzae, S. zeamais; Sphenophorus spp. such as S. levis; Stegobium pani- ceum, Sternechus spp. such as S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. such as T.
castaneum; Trogoderma spp., Tych/us spp., Xylotrechus spp. such as X. pyrrhoderus; and, Zabrus spp. such as Z. tenebrioides;
insects from the order of Diptera for example Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bac- trocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis ca- pitata, Chrysomyia spp. such as C. bezziana, C. hominivorax, C. macellaria; Chrysops at/anti- cus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as C. hominivorax; Contarinia spp. such as C. sorghicola; Cordylobia anthropophaga, Culex spp. such as C. nigripalpus, C. pip/ens, C quinquefasciatus, C tarsalis, C tritaeniorhynchus; Culicoides furens, Culiseta inor- nata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasineura oxycoccana, Delia spp. such as D. antique, D. coarctata, D. platura, D. radicum; Dermatobia hominis, Drosophila spp. such as D. suzukii, Fannia spp. such as F. canicularis; Gastraphilus spp. such as G. intestinalis; Geomyza tipunctata, Glossina spp. such as G. fusci- pes, G. morsitans, G. pa/pa/is, G tach/noides; Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. such as H. platura; Hypoderma spp. such as H. lineata; Hyppo- bosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp. such as L. sativae, L. trifolii; Lucilia spp. such as L. caprina, L. cuprina, L. sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as M. destructor; Musca spp. such as M. autumnalis, M. domestical Muscina stabulans, Oestrus spp. such as O. ovis; Opomyza florum, Oscinella spp. such as O. frit; Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. such as P. ant/qua, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimu/ium mixtum, Psi/a rosae, Psorophora co/umbiae, Psorophora disco/or, Rhago/etis spp. such as R. cerasi, R. cingu/ate, R. indifferens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp. such as S. hae- morrhoidalis; Simulium vittatum, Sitodiplosis mosellana, Stomoxys spp. such as S. calcitrans; Tabanus spp. such as T. atratus, T. bovinus, T. lineola, T. similis; Tannia spp., Thecodiplosis japonensis, Tipula oleracea, Tipula paludosa, and Wohlfahrtia spp;
insects from the order of Thysanoptera for example, Baliothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femora/is, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. such as S. citri, S. dorsalis, S. perseae;
Stenchaetothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp. such as T. imagines, T. hawaiiensis, T. oryzae, T. pa/mi, T. parvispinus, T. tabaci;
insects from the order of Hemiptera for example, Acizzia jamatonica, Acrosternum spp. such as A. a e/Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsu- gae, Adelphocoris spp., such as A. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Aulacorthum solani, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolo- bus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. such as A. craccivora, A. fabae, A. forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pom/, A. sambuci, A.
schneideri, A. spiraeco/a; Arbor/d/a apica/is, Ari/us cr/tatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacaspis yasumatsui, Aulacorthum solani, Bactericera cockerel// (Paratrioza cockerelli), Bemisia spp. such as B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp. such as B. leucopterus; Brachycaudus spp. such as B. cardui, B. helichrysi, B. persicae, B. prunicola; Brachycolus spp., Brachycorynella asparagi, Brevicoryne brassicae, Cacopsylla spp. such as C fulguralis, C pyricola (Psylla piri); Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horn/, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tega- lensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Cimex spp. such as C hemipterus, C lectularius; Coccomytilus halli, Coccus spp. such as C hesperi- dum, C pseudomagno/iarum, Corythucha arcuata, Creont/ades d/iutus, Cryptomyzus ribis, Chrysomphalus aonidum, Cryptomyzus ribis, Ctenarytaina spatulata, Cyrtopeltis notatus, Dalbu- lus spp., Dasynus piperis, Dialeurodes spp. such as D. citrifolii; Dalbulus maidis, Diaphorina spp. such as D. citri; Diaspis spp. such as D. bromeliae; Dichelops furcatus, Diconocoris he- wetti, Dora/is spp., Dreyfus/a nordmann/anae, Dreyfus/a p/ceae, Drosicha spp., Dysaphis spp. such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudoso/ani, Dysdercus spp. such as D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Em- poasca spp. such as E. fabae, E. so/ana; Ep/d/asp/s leperii, Eriosoma spp. such as E. lanige- rum, E. pyricola; Erythroneura spp., Eurygaster spp. such as E. integriceps; Euscelis bilobatus, Euschistus spp. such as E. heros, E. impictiventris, E. servus; Fiorinia theae, Geococcus coffeae, Glycaspis brimblecombei, Halyomorpha spp. such as H. halys; Heliopeltis spp., Homalodisca vitripennis (=H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lactucae, lcerya spp. such as I. purchase; Idiocerus spp., Idioscopus spp., Laodelphax stria- tellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptoco- risa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineo- laris, L. pratensis; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macro- siphum spp. such as M. rosae, M. avenae, M. euphorbiae; Macrosteles quadrilineatus, Maha- narva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Melanocallis (=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzocallis coryli, Murgantia spp., Myzus spp. such as M. ascalonicus, M. cerasi, M. nicotianae, M. persicae, M. varians; Nasonovia r ibis- nig ri, Neo- toxoptera formosana, Neomegalotomus spp, Nephotettix spp. such as N. malayanus, N. nigro- pictus, N. parvus, N. virescens; Nezara spp. such as N. viridula; NHaparvata lugens, Nysius button/, Oebaius spp. such as O. pugnax; Oncometopia spp., Orthezia praelonga, Oxycaraenus hyalinipennis, Parabemisia myricae, Parlatoria spp., Parthenolecanium spp. such as P. corn/, P. persicae; Pemphigus spp. such as P. bursarius, P. populivenae; Peregrinus maidis, Perkinsiella saccharic/da, Phenacoccus spp. such as P. acer/s, P. gossyp/i; Ph/oeomyzus passer/n/i, Phoro- don humu/i, Phylloxera spp. such as P. devastatrix, Piesma quadrata, Piezodorus spp. such as P. guildinii; Pinnaspis aspidistrae, Planococcus spp. such as P. citri, P. ficus; Prosapia bicincta, Protopulvinaria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as P. comstocki; Psylla spp. such as P. mail; Pteroma/us spp., Pu/vi- nar/a amygda/i, Pyr/i/a spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. such as R. pseudobrass/cas, R. insertum, R. maidis, R. pad/; Sagatodes spp., Sahlbergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mali, Scaptocoris spp., Scaphoides titanus, Schizaphis graminum, Schizoneura lanuginosa, Scoti- nophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solu- bea ins u laris, Spissistilus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis pyri- oides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis macu- late, Thyanta spp. such as T. accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeurodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii,
Insects from the order Hymenoptera for example Acanthomyops interjectus, Athalia rosae, Atta spp. such as A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A.
sexdens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp. such as C. florida- nus, C. pennsylvanicus, C. modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmex spp., Dryocos- mus kuriphilus, Formica spp., Hoplocampa spp. such as H. minuta, H. testudinea; Iridomyrmex humilis, Lasius spp. such as L. niger, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp. such as M. pharaonis, Monomorium, Nylandria fulva, Pachycondyla chinen- sis, Paratrechina longicornis, Paravespula spp., such as P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. such as P. megacephala; Pogonomyrmex spp. such as P. barbatus, P. californicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cyaneus, Solenopsis spp. such as S. geminata, S.invicta, S. molesta, S. richteri, S. xyloni, Sphecius speciosus, Sphex spp., Tapinoma spp. such as T melanocephalum, T sessile; Tetra- morium spp. such as T caespitum, T bicarinatum, Vespa spp. such as V. crabro; Vespula spp. such as V. squamosal; Wasmannia auropunctata, Xylocopa sp; Insects from the order Orthoptera for example Acheta domesticus, Calliptamus italicus, Chor- toicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp. such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. such as L. migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris sep- temfasciata, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp. such as S. ameri- cana, S. gregaria, Stemopelmatus spp., Tachycines asynamorus, and Zonozerus variegatus;
Pests from the Class Arachnida for example Acari,e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (e.g. A. americanum, A. variegatum, A. maculatum), Argas spp. such as A. persicu), Boophilus spp. such as B. annulatus, B. decoloratus, B. micro- plus, Dermacentor spp. such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as /. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacifi- cus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. such as P. ovis, Rhipicephalus spp. such as R. sanguineus, R. appendiculatus, Rhipicephalus everts/, Rhizo- glyphus spp., Sarcoptes spp. such asS. Scabiei, and Family Eriophyidae including Acer/a spp. such as A. sheldoni A. anthocoptes, Acallitus spp., Aculops spp. such as A. iycopersici, A. pe- lekassr, Aculus spp. such as A. schlechtendali; Colomerus vltis, Epitrlmerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp. such as Eriophyes sheldonr, Family Tarsonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Steno- tarsonem us spp. Steneotarsonemus spinki, Family Tenuipalpidae including Brevipalpus spp. such as B. phoenicis; Family Tetranychidae including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranych us spp. such as T. cinnabarinus, T. evansi, T. kan- zawai, T, pacificus, T. phaseulus, T. telarius and T. urticae, Bryobia praetiosa; Panonychus spp. such as P. u/mi, P. citri, Metatetranychus spp. and Oligonychus spp. such as O. pratensis, O. perseae, Vasates Iycopersici, Raoiella indica, /¾/77/7yCarpoglyphidae including Carpoglyphus spp.; Pentha/eidae spp. such as Halotydeus destructor, Family Demodicidae with species such as Demodexspp.; Family Trombicidea including Trombicula spp:, Family Macronyssidae including Ornothonyssus spp:, Family Pyemotidae including Pyemotes tritici, Tyrophagus putrescen- tiae; Family Acaridae including Acarus siro; Family Araneida including Latrodectus mactans, Tegenaria agrestis, Chiracanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles rec/usa;
Pests from the Phylum Nematoda, for example, plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nema- todes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H. glycines, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp:, Stem and foliar nematodes, Aphelenchoides spp. such as A. besseyi; Sting nematodes, Belonolaim us spp. such as B. longi- caudatus; Pine nematodes, Bursaphelenchus spp. such as B. lignicolus, B. xylophilus; Ring nematodes, Criconema spp., Criconemella spp. such as C. xenoplax and C. ornata; and, Crico- nemoides spp. such as Criconemoides informis; Mesocriconema spp.; Stem and bulb nematodes, Ditylench us spp. such as D. destructor, D. dipsaci; Awl nematodes, Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; Sheath and sheathoid nematodes, Hemicy- cliophora spp. and Hemicriconemoides spp. ; Hirshmanniella spp. / Lance nematodes, Hoplo- aimus spp.; False rootknot nematodes, Nacobbus spp.; Needle nematodes, Longidorus spp. such as L. elongatus; Lesion nematodes, Pratylenchus spp. such as P. brachyurus, P. neglect- tus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nematodes, Radopholus spp. such as R. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp. such as
R. robustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. such as T. obtusus, T. primitivus; Paratrichodorus spp. such as P. minor; Stunt nematodes, Tylenchor- hynchus spp. such as T. c/aytoni, T. dub/us; Citrus nematodes, Tylenchulus spp. such as T. se- mipenetrans; Dagger nematodes, Xiphinema spp.; and other plant parasitic nematode species; Insects from the order Isoptera for example Calotermes flavicollis, Coptotermes spp. such as
C. formosanus, C. gestroi, C. acinaciformis; Cornitermes cumulans, Cryptotermes spp. such as C. brevis, C. cavifrons; Globitermes sulfureus, Heterotermes spp. such as H. aureus, H. longi- ceps, H. tenuis; Leucotermes flavipes, Odontotermes spp., Incisitermes spp. such as /. minor, I.
Snyder, Marginitermes hubbardi, Mastotermes spp. such as M. darwiniensis Neocapritermes spp. such as N. opacus, N. parvus; Neotermes spp., Procornitermes spp., Zootermopsis spp. such as Z. angusticollis, Z. nevadensis, Reticulitermes spp. such as R. hesperus, R. tibia/is, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virginicus; Termes natalensis, Insects from the order Blattaria for example Blatta spp. such as B. orientalis, B. lateralis;
Blattella spp. such as B. asahinae, B. germanica; Leucophaea maderae, Panchlora nivea,
Periplaneta spp. such as P. americana, P. australasiae, P. brunnea, P. fuligginosa, P. japonica;
Supella longipalpa, Parcoblatta pennsylvanica, Eurycotis floridana, Pycnoscelus surinamensis, Insects from the order Siphonoptera for example Cediopsylla simples, Ceratophyllus spp.,
Ctenocephalides spp. such as C. felis, C. canis, Xenopsylla cheopis, Pulex irritans,
Trichodectes canis, Tunga penetrans, and Nosopsyllus fasciatus,
Insects from the order Thysanura for example Lepisma saccharina , Ctenolepisma urbana, and Thermobia domestica,
Pests from the class Chilopoda for example Geophilus spp., Scutigera spp. such as Scutigera coleoptrata;
Pests from the class Diplopoda for example Blaniulus guttulatus, Ju/us spp., Narceus spp., Pests from the class Symphyla for example Scutigerella immaculata,
Insects from the order Dermaptera, for example Forficula auricularia,
Insects from the order Collembola, for example Onychiurus spp., such as Onychiurus armatus, Pests from the order Isopoda for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber,
Insects from the order Phthiraptera, for example Damalinia spp., Pedicuius spp. such as Pedicuius humanus capitis, Pedicuius humanus corporis, Pedicuius humanus humanus; Pthirus pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus suis;
Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp.,
Examples of further pest species which may be controlled by mixtures of the invention include: from the Phylum Mollusca, class Bivalvia, for example, Dreissena spp:, class Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Ga/ba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, Succinea spp.; from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancy- lostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooper/a spp., Dicrocoelium spp., Dictyocaulus filaria, Di- phyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp. such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragoni- mus spp., Schistosomen spp., Strongyloides fuelleborni, 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 present inventon are particularly suitable for controlling the following plant diseases:
Albugo spp. (white rust) on ornamentals, vegetables (e. g. A Candida) and sunflowers (e. g. A tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A brassicola or brassicae), sugar beets (A tenuis), fruits, rice, soybeans, potatoes (e. g. A so/an/ or A. alternate), tomatoes (e. g. A so/ani or A a/ternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A / /f/c/ (anthracnose) on wheat and A horde/ on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (Z7. maydis) or Northern leaf blight (.5. zeico/a) on corn, e. g. spot blotch (z5. sorokiniana) on cereals and e. g. z5. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fucke/iana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi(Ou\ch elm disease) on elms; Cercos- pora spp. (Cercospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum. leaf mold) and cereals, e. g. C. her- barum (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. sati- vus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colleto- trichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminico/a: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasak/i (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendri. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chla- mydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits {E. pyrl), soft fruits {E. veneta: anthracnose) and vines {E. ampe/ina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. so/ani( 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; G 'uignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vasta- trix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macro- phomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. ββίΜθίοή, tobacco {P. tabacina) and soybeans (e. g. P. manshurica); Phakop- sora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping- off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. vitico/a: 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); P/asmodiophora brassicae (club root) on cabbage, rape, radish and other plants; P/asmopara spp., e. g. P. vitico/a (grapevine downy mildew) on vines and P. ha/stedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Po/ymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapes/a yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. hum/lion hop; Pseudopezicu/a 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. horde/ (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. kuehn// '(orange rust) on sugar cane and P. asparag/ on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soy- beans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanider- matum); Ramularia spp., e. g. R. co/lo-cygni (Ramu\ar\a leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. so/an/ (root and stem rot) on soybeans, R. solan/' (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rh/zopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonos- pora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthospo- rium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn.
Phaeosphaer/a] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoll) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis. corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes. 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. 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, 21-22):
XY
E = X + Y
Too 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. The analysis of synergism or antagonism between the mixtures or compositions was determined using Colby's equation.

Claims

Claims Pesticidal mixtures comprising as active components 1 ) at least one active compound of formula I: wherein R1 is H, Ci-C2-alkyl, or Ci-C2-alkoxy-Ci-C2-alkyl; R2 is CH3, or halomethyl; R3 is CN, d-Ce-alkyl, Ci-C6-haloalkyl, Ci-C2-alkoxy-Ci-C2-alkyl, C2-C6-alkenyl and C2-C6-alkynyl, C3-C6-cycloalkyl, Cs-Ce-cycloalkenyl, Ci-C6-alkoxy, wherein the C-atoms are unsubstituted, or partially or fully substituted by Ra, Ra is halogen, CN, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C4-alkoxy, Ci-C2-haloalkoxy; R4 is Ci-C4-alkyl, or a group mentioned for R3; or R3 and R4 may together form Cs-Ce-cycloalkyl, which is unsubstituted, or partially or fully substituted by Ra; R5 is H, or a group mentioned for R4; and the stereoisomers, salts, tautomers and N-oxides thereof; and 2) at least one biopesticide II selected from the groups L1 to L5: L1 ) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana, Clavibacter michiganensis(bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f . catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor a/bus, Paenibacillus alvei, Paenibacillus polymyxa, Pantoea vagans, Penicillium bilaiae, P.steckii, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain); L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract; L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bass/ana, B. brongniartii, Burkho/deria sp., Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobacterium sp., Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhedrovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L muscarium, Metarhizium anisopliae, Metarhizium anisopliae var. anisop/iae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. ///acinus, Paenibacillus popilliae, Pasteur/a sp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces galbus, S. micro f/avus; L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,1 1 ,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1- butanol, methyl eugenol, methyl jasmonate, jasmonic acid or salts or derivatives thereof, (E,Z)-2,13-octadecadien-1 -ol, (E,Z)-2,13-octadecadien-1-ol acetate, (E,Z)- 3,13-octadecadien-1-ol, R-1 -octen-3-ol, pentatermanone, (E,Z,Z)-3,8,1 1-tetradeca- trienyl acetate, (Z,E)-9,12-tetradecadien-1-yl acetate, Z-7-tetradecen-2-one, Z-9-te- tradecen-1 -yl acetate, Z-1 1 -tetradecenal, Z-1 1-tetradecen-1-ol, extract of Chenopodium ambrosiodes, Neem oil, Quillay extract; L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity: Azospinilum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp., B. elkanii, B. japo- nicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium sp., Rhizobium ieguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropic/, Sinorhizobium meliloti; in synergistically effective amounts. The mixtures according to claim 1 , wherein component 1 ) and component 2) are present in a total weight ratio of from 100:1 to 1 :100 wherein the total weight of component 2) is based on the amount of the solid material (dry matter) of component 2). The mixtures according to any of the claims 1 or 2, wherein component 1 ) is selected from compounds of formula I, wherein R2 is CH3 and R5 is H, said compounds being compounds of formula IA: IA. The mixtures according to any one of claims 1 to 3, wherein component 1 ) is selected from the following formula IA compounds 1-1 to 1-18 listed below: The mixtures according to any one of claims 1 to 4, wherein component 2) is selected fromL1 ) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pull u Ian s, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f . catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor a/bus, Paenibacillus alvei, Paenibacillus polymyxa, Pantoea vagans, Penicillium bilaiae, P.steckii, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas ch/oraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T. asperellum, T. a tro viride, T. fertile, T. gams/I, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia; L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract; L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, Burkho/deria sp., Chromobacterium subtsugae, Flavobacterium sp., Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteur/a sp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Streptomyces galbus, S. micro flavus, L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: cis-jasmone, methyl jasmonate, jasmonic acid or salts or derivatives thereof; L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp., B. elkanii, B. japo- nicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium sp., Rhizobium leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti; and is preferably selected from the group L3. The mixtures according to any one of claims 1 to 5, wherein component 2) is selected from Bacillus firmus, Pasteur/a nishazawa sp., Flavobacterium sp., Paecilomyces ///acinus, and Burkholderia sp. The mixtures according to any one of claims 1 to 6, wherein component 2) is selected from Bacillus firmus, Pasteuria nishizawa, and F/avobacterium sp., in particular from the strains Bacillus firmus CNCM 1-1582, Pasteuria nishizawae Pn , and Flavobacterium sp. H492. The mixtures according to any of the claims 1 to 7, further comprising as active component 3) a further active compound III, which is selected from insecticides or fungicides. The mixtures according to claim 8, wherein the active component 3) is an insecticide, wherein said insecticide is selected from the group consisting of fipronil, clothianidin, thiamethoxam, acetamiprid, dinotefuran, imidacloprid, thiacloprid, sulfoxaflor, methiocarb, tefluthrin, bifenthrin, cypermethrin, alphacypermethrin, spinosad, cyantraniliprole, chlorantraniliprole, triflumezopyrim, flupyradifurone, abamectin, thiodicarb, tetraniliprole, and tioxazafen. 0. The mixtures according to claim 8, wherein the active component 3) is a fungicide, wherein said fungicide is selected from the group consisting of azoxstrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, sedaxane, penthiopyrad, penflufen, fluopyram, fluxapyroxad, boscalid, oxathiapiprolin, metalaxyl, metalaxyl-M, ethaboxam, dimethomorph, cyproconazole, difenoconazole, prothioconazole, flutriafol, thiabendazole, ipconazole, tebuconazole, triadimenol, prochloraz, fluquinconazole, triticonazole, fludioxonil, carboxin, silthiofarm, ziram, thiram, carbendazim, thiophanate methyl, fenamidone, hymexazol, and fluazinam.
1. A seed treatment composition comprising an auxiliary and a mixture as defined in any one of claims 1 to 10, wherein the auxiliary is preferably selected from the group consisting of surfactants, antifreezing agents, binders, and pigments, and is particularly preferably a surfactant or a binder.
2. The seed treatment composition according to claim 1 1 , which is in the form of a flowable concentrate FS, a solution LS, a powder for dry treatment DS, a water dispersible powder for slurry treatment WS, a water-soluble powder SS, an emulsion ES or EC, or a gel formulation, and is preferably in the form of a flowable concentrate.
Use of a mixture as defined in any one of claims 1 to 10 or a seed treatment composition as defined in claim 1 1 or 12 for protecting a plant, plant propagation material, or soil or water, in which the plants are growing, against the attack or infestation by invertebrate pests.
A method for controlling invertebrate pests, which method comprises contacting the plant or the plant propagation material or the soil; the pests or their food supply, habitat or breeding grounds, with a pesticidally effective amount of a mixture as defined in any one of claims 1 to 10 or with a seed treatment composition as defined in claim 1 1 or 12.
5. Seeds comprising the mixture as defined in any one of claims 1 to 10 or the seed
treatment composition as defined in 1 1 or 12 in an amount of from 0.01 g to 10000 g per 100 kg of seeds.
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