GB2481118A - Pesticidal mixtures comprising enantiomerically enriched isoxazoline derivatives - Google Patents

Pesticidal mixtures comprising enantiomerically enriched isoxazoline derivatives Download PDF

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GB2481118A
GB2481118A GB1109466.1A GB201109466A GB2481118A GB 2481118 A GB2481118 A GB 2481118A GB 201109466 A GB201109466 A GB 201109466A GB 2481118 A GB2481118 A GB 2481118A
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Prior art keywords
component
thiodicarb
compound selected
sulfoxaflor
abamectin
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GB201109466D0 (en
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Jerome Yves Cassayre
Elvira Molitor
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Syngenta Participations AG
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Syngenta Participations AG
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms

Abstract

Pesticidal mixtures comprising a components A, B and C, wherein component A is an enantiomeric mixture of a compound of formula I that is enantiomerically enriched for the S enantiomers wherein the symbol * indicates the chiral centre; A1 and A2 are C-H, or one of A1 and A2 is C-H and the other is N; R1 is a carboxamide-linked group or 1,2,4-trizolyl; R2 is chlorodifluoromethyl or trifluoromethyl; R3 is 3,5-dibromo-phenyl, 3,5-dichloro-phenyl, 3,4-dichloro-phenyl, 3,5-dichloro-4- fluoro-phenyl or 3,4,5-trichloro-phenyl; R4 is hydrogen, methyl or cyano; R5 is hydrogen; or R4 and R5 together form a bridging 1,3-butadiene group; component B is a pesticide compound and component C is a compound selected from an insecticide, a fungicide and a nematicide, wherein components B and C are different. The mixture is useful in controlling phytopathogenic diseases and controlling insects, acarines, nematodes or molluscs on useful plants.

Description

PESTICIDAL MIXTURES
The present invention relates to mixtures of pesticidally active ingredients and to methods
of using the mixtures in the field of agriculture.
EP 1731 512 discloses that certain isoxazoline compounds have insecticidal activity. WO 2010/003877 and WO 2010/003923 disclose various pesticidal mixtures comprising certain isoxazoline compounds.
The present invention provides pesticidal mixtures comprising a component A, a component B, and a component C, wherein component A is an enantiomeric mixture of a compound of formula I that is enantiomerically enriched for the S enantiomer
A
wherein the symbol * indicates the chiral centre; A and A2 are C-H, or one of A1 and A2 is C-H and the other is N; R' is a group selected from P1 to P11 CF3 c3 y0 P5 P6
H yNy -LCF3
Plo P11 R2 is chiorodifluoromethyl or trifluoromethyl; R3 is 3,5-dibromo-phenyl, 3,5 -dichloro-phenyl, 3,4-dichloro-phenyl, 3,5-dichloro-4-fluoro-phenyl or 3,4,5-tnchloro-phenyl; R is hydrogen, methyl or cyano; R5 is hydrogen; or R4 and R5 together form a bridging I,3-butadiene group; component B is a compound selected from Tefluthrin, Lambda-cyhalothrin, Abamectin, Spinosad, Spinetoram, Chiorpyrifos, Thiodicarb, Chiorantraniliprole, Cyantranil iprole, Bacillus firmus, Bacillus subtil is, Pasteuria penetrans, I midacloprid, Thiacloprid, Acetamiprid, Ni tenpyram, Dinotefuran, Thiamethoxani, Clothianidin, Nithiazine, Flonicamid, Fipronil, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat; and component C is a compound selected from an insecticide, a fungicide and a nematicide, which insecticide is selected from neonicotinoids, carbamates, diamides, spinosyns, phenylpyrazoles, pyrethroids, Pyrifluquinazone, Pymetrozine, Sulfoxafior and Spirotetramat; which fungicide is selected from Azoxystrobin, Trifloxystrobin, Fluoxastrobin, Cyproconazole, Difenoconazole, Prothioconazole, Tebuconazole, Triticonazole, Fludioxonil, Thabendazole, Ipeonazole, Cyprodinil, Myclobutanil, Metalaxyl, Mefcnoxam, Sedaxane, Fluopyram, Penflufen, Fuxapyroxad and Penthiopyrad; which nematicide is selected from avermectin (e.g., Abamectin), carbamate nematicides organophosphorus nematicides, Captan, Thiophanate-methyl and Thiabendazole a compound of formula X, wherein n is 0, 1 or 2 and the thiazole ring may be optionally substituted, Bacillus flrmus, Bacillus cereus, Bacillus subtilis, and Pasteuria penetrans; wherein components B and C are different.
Compounds of formula I are known to have insecticidal activity. Certain active ingredient mixtures of a compound of formula I and additional active ingredients can enhance the spectrum of action with respect to the pest to be controlled, e.g. the animal pest and/or the fungal pest. For example, the combination of A, B and C may cause an increase in the expected insecticidal action and/or fungicidal action. This allows, on the one hand, a substantial broadening of the spectrum of pests that can be controlled and, on the other hand, increased safety in use through lower rates of application.
However, besides the actual synergistic action with respect to pest control, the pesticidal mixtures according to the invention can have further advantageous properties which can also be described, in a wider sense, as synergistic activity. Examples of such advantageous properties that may be mentioned are: a broadening of the spectrum of activity; a reduction in the rate of application of the active ingredients; adequate pest control with the aid of the mixtures according to the invention, sometimes even at a rate of application at which the individual compounds are totally ineffective; advantageous behaviour during formulation and/or upon application, for example upon grinding, sieving, emulsifying, dissolving or dispensing; increased storage stability; improved stability to light; more advantageous degradability; improved toxicological and/or ecotoxicological behaviour; improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination; or any other advantages familiar to a person skilled in the art.
Compounds of formula I as racemic mixtures are known e.g. EP 1731512, WO 2010/003877 and WO 2010/003923. Methods of preparing enantiomerically enriched mixtures are described for example in WO 2009/0639 10. The components B and C are known, e.g. from "The Pesticide Manual", Fifteenth Edition, Edited by Clive Tomlin, British Crop Protection Council.
The mixtures of the invention may also comprise other active ingredients in addition to components A, B and C. In other embodiments the mixtures of the invention may include only components A, B and C (or A, B, Cl and C2) as pesticidally active ingredients.
Preferred substituents are, in any combination, as set out below.
R2 is preferably trifluoromethyl.
R3 is preferably 3,5-dichloro-phenyl or 3,4,5-trichiorophenyl.
R4 is preferably methyl or -CN, more preferably R4 is methyl when R' is a group other than P3 and R4 is -CN when R4 is P3.
R5 is preferably hydrogen.
Each substituent definition in each alternative preferred groups of compounds of formula 1 may be juxtaposed with any substituent definition in any other preferred group of compounds, in any combination.
Compounds of formula I include at least one chiral centre and may exist as compounds of formula 1* or compounds of formula j** ( Generally compounds of formula 1*1 (i.e. the S enantiomer) are more biologically active than compounds of formula 1* (i.e. the R enantiomer).
S Component A according to the invention is an enantiomeric mixture that is enantiomerically enriched for the compound of formula I". Enantiomerically enriched means that the molar proportion of one enantiomer in the mixture compared to the total amount of both enantiomers is greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or least 99%. In one embodiment component A is a compound of formula 1' in substantially pure form, e.g. it is provided substantially in the absence of the alternative enantiomer.
Preferred compounds of formula 1 are shown in the Table below.
Table I: Compounds of formulaiial (Ia) The symbol * indicates the location of the chiral centre No. Stereochemistry at * I 00 -çj o o ot o ZI z ZI ZI ZI ZI ZI ::.::° NCF3 Bearing in mind the chiral centre referred to above, the present invention otherwise includes all isomers of compounds of formula (I) and salts thereof, including enantiomers, diastereomers and tautomers.
In one embodiment of the invention component C is an insecticide which is selected from neonicotinoids, carbamates, diamides, spinosyns, phenylpyrazoles, pyrethroids, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetrainat. Examples of neonicotinoids are Thiamethoxam, Clothianidin, Imidacloprid, Acetamiprid, Dinotefuran, Nitenpyram, Nithiazine, Flonicamid and Thiacloprid. Preferred neonicotinoids are Thianiethoxam, Imidacloprid and Clothianidin. Examples of carbamates include Thiodicarb, Aldicarb, Carbofuran, Furadan, Fenoxycarb, Carbaryl, Sevin, Ethienocarb, and Fenobucarb. Examples of diamides include Chiorantraniliprole, Cyantraniliprole, and Flubendiamide. Examples of spinosyns include Spinosad and Spinetoram. Examples of IS pyrethoids include Cyhalothrin, Lambda-cyhalothrin, Gamma-cyhalothrin, and Tefluthrin. An example of phenylpyrazole is Fipronil.
In another embodiment of the invention component C is a fungicide. The fungicide is preferably selected from Azoxystrobin, Trifloxystrobin, Fluoxastrobin, Cyproconazole, Difenoconazole, Prothioconazole, Tebuconazole, Tnticonazole, Fludioxonil, Thiabendazole, lpconazole, Cyprodinil, Myclobutanil, Metalaxyl, Mefenoxam (also known as Metalaxyl-M), Sedaxane, Fluopyram, Penflufen, Fuxapyroxad and Penthiopyrad.
In another embodiment of the invention component C is a nematicide. The nematicide can be any nematicide known in the art. Examples include an Avermectin (e.g., Abamectin), carbamate nematicides (e.g., Aldicarb, Thiodicarb, Carbofuran, Carbosulfan, Oxamyl, Aldoxycarb, Ethoprop, Methomyl, Benomyl, Alanycarb, Iprodione), organophosphorus nematicides (e.g., Phenamiphos (Fenamiphos), Fensulfothion, Terbulos, Fosthiazate, Dimethoate, Phosphocarb, Dichiofenthion, Isamidofos, Fosthietan, Isazofos Ethoprophos, Cadusafos, Terbufos, Chiorpyrifos, Dichiofenthion, Heterophos, Isamidofos, Mecarphon, Phorate, Thionazin, Triazophos, Diamidafos, Fosthietan, Phosphamidon, Imicyafos), and certain fungicides, such as Captan, Thiophanate-methyl and Thiabendazole. Also included as a nematicide is a compound of formula X, wherein n is 0, 1 or 2 and the thiazole ring may be optionally substituted. Abamectin, Aldicarb, Thiodicarb, Dimethoate, Methomyl, a compound of formula X and Oxamyl are preferred nematicides for use in this invention.
In addition, nematicidally active biological agents can be included in the compositions of the invention. The nematicidally active biological agent refers to any biological agent that has nematicidal activity. The biological agent can be any type known in the art including bacteria and fungi. The wording "nematicidally active" refers to having an effect on, such as reduction in damage caused by, agricultural-related nematodes. The nematicidally active biological agent can be a bacterium or a fungus. Preferably, the biological agent is a bacterium. Examples of nematicidally active bacteria include Bacillus firmus, Bacillus cereus, Bacillus subtilis, and Pasteuria penetrans. A suitable Bacillus firmus strain is strain CNCM 1-1582 which is commercially available as BioNemTM. A suitable Bacillus cereus strain is strain CNCM 1-1562. Of both Bacillus strains more details can be found in US 6,406,690.
In one embodiment component C is a compound selected from Thiamethoxam, Clothianidiri, Nithiazine, Flonicamid, Imidacloprid, Acetamiprid, Dinotefuran, Nitenpyram, Thiacloprid, Thiodicarb, Aldicarb, Carbofuran, Furadan, Fenoxycarb, Carbaryl, Sevin, Ethienocarb, Fenobucarb, Chiorantraniliprole, Cyantraniliprole, Flubendiamide, Spinosad, Spinetoram, Cyhalothrin, Lambda-cyhalothrin, Gamma-cyhalothrin, Tefluthrin, Fiproni 1, Azoxystrobin, Tn floxystrobin, Fluoxastrobin, Cyprocoriazole, Difenoconazole, Prothioconazole, Tebuconazole, Triticonazole, Fludioxoni 1, Thiabendazole, lpconazole, Cyprodini I, Myclobutani I, Metalaxyl, Mefenoxam, Sedaxane, Fluopyram, Penflufen, Fuxapyroxad, Abamectin, Aldicarb, Thiodicarb, Carbofuran, Carbosulfan, Oxamyl, Aldoxycarb, Ethoprop, Methomyl, Benomyl, Alanycarb, Iprodione, Phenamiphos, Fensulfothion, Terbufos, Fosthiazate, Dimeihoate, Phosphocarb, Dichiofenthion, Isamidofos, Fosthietan, Isazofos, Ethoprophos, Cadusafos, Terbufos, Chlorpyrifos, Dichiofenthion, Heterophos, Isamidofos, Mecarphon, Phorate, Thionazin, Triazophos, Diamidafos, Fosthietan, Phosphamidon, Imicyafos, Captan, Thiophanate-methyl, Thiabendazole, a compound of formula X, Pyrifluquinazone, Pyrnetrozine, Sulfoxaflor and Spirotetramat, Bacillus firmus, Bacillus subtilis and Pasteuria penetrans. I0
In one embodiment component C is a compound selected from Tefluthrin, Lambda-cyhalothrin, Abamectin, Spinosad, Spinetoram, Chiorpyrifos, Thiodicarb, Chiorantraniliprole, Cyantraniliprole, Bacillus litmus, Bacillus subtilis, Pasteuria penetrans, Imidacloprid, Thiacloprid, Acetamiprid, Nitenpyram, Dinotefuran, Thiamethoxam, Clothianidin, Nithiazine, Flonicamid, Fipronil, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat, wherein components B and C are different.
In one embodiment component B is a compound selected from Tefluthrin, Lambda-cyhalothrin, Abamectin, Spinosad, Spinetoram, Chlorpyrifos, Thiodicarb, Chlorantraniliprole, Cyantraniliprole, Bacillus firmus, Bacillus subtilis and Pasteuria penetrans; and component C is a compound selected from Imidacloprid, Thiacloprid, Acetamiprid, Nitenpyram, Dinotefuran, Thiamethoxam, CLothianidin, Nithiazine, Flonicamid, Fipronil, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat.
In a further embodiment component B is a compound selected from Tefluthrin, Lambda-cyhalothrin, Abamectin, Spinosad, Spinetoram, Chlorpyrifos, Thiodiearb, Chiorantraniliprole, Cyantraniliprole, Bacillus firmus, Bacillus subtilis and Pasteuria penetrans; and component C is a compound selected from Sedaxane, Fludioxonil, Metalaxyl, Mefenoxam, Cyprodinil, Azoxystrobin, Tebuconazole, Difenoconazole, Thiabendazole, Fluopyram, Penflufen and Fuxapyroxad.
In yet another embodiment component B is a compound selected from Imidacloprid, Thiacloprid, Acetamiprid, Nitenpyram, Dinotefuran, Thiamethoxam, Clothianidin, Nithiazi ne, Flonicamid, Fipronil, Pyrifluquinazone, Pymetrozine, Sul foxaflor and Spirotetramat; and component C is a compound selected from Sedaxane, Fludioxonil, Metalaxyl, Mefenoxam, Cyprodinil, Azoxystrobin, Tebuconazole, Difenoconazole, Thiabendazole, Fluopyram, Penflufen and Fuxapyroxad.
in yet another embodiment component B is a compound selected from Tefluthrin, Lambda-cyhalothrin, Abamectin, Spinosad, Spinetoram, Chiorpyrifos, Thiodicarb, Chiorantraniliprole, Cyantraniliprole, Bacillus firmus, Bacillus subtilis and Pasteuria penetrans; and wherein the mixture comprises as component C, component CI and component C2, wherein component CI is a compound selected from Imidacloprid, Thiacloprid, Acetamiprid, Nitenpyraim Dinotefuran, Thiamethoxam, Clothianidin, Nithiazine, Flonicamid, Fipronil, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetrainat; and component C2 is a compound selected from Sedaxane, Fludioxonhl, Metalaxyl, Mefenoxam, Cyprodinil, Azoxystrobin, Tebuconazole, Difenoconazole, Thiabendazole, Fluopyram, Penflufen and Fuxapyroxad.
The invention also relates to the following combinations:
AB C AB C
TI Tefluthrin Imidacloprid Ti Lambda-cyhalothrin Imidacloprid Ti Tefluthrin Thiacloprid TI Lambda-cyhalothrin Thiacloprid Ti Tefluthrin Acetamiprid Ti Lambda-cyhalothrin Acetaniiprid TI Tefluthrin Nitenpyram Ti Lambda-cyhalothrin Nitenpyram Ti Tefluthrin Dinotefuran TI Lambda-cyhalothrin Dinotefuran -Ti Tcfluthrm Thiamethoxam TI Lambda-cyhalothrin Thiamethoxai TI Tefluthrin Clothianidin -TI Lambda-cyhalothrifl Clothianidin Ti Tefluthrin Nithiazinc TI Lambda-cyhalothrin Nithiazine TI Tefluthrin Flonicamid TI Lambda-cyhalothrin Flonicamid Ti Tefluthrin Fipronil TI Lambda-cyhalothrin Fipronil TI Tefluthrin Pyrifluquin-TI Lambda-cyhalothrin Pyrifluquin-azone -_________________ azone TI Tefluthrin Pymetrozine Ti Lambda-cyhalothrin Pymetrozine Ti Tefluthrin Sulfoxaflor --TI Lambda-cyhatothrin Sulfoxaflor TI Tefluthrin Spirotetramat TI Lambda-cyhalothrin Spirotetramat TI Abamectin Imidacloprid TI Spinosad lmidacloprid TI Abamectin Thiacloprid TI Spinosad Thiacloprid TI Abamectin Acetamiprid TI Spinosad Acetamiprid TI Abamectin Nitenpyrani TI Spinosad Nitenpyram TI Abaniectin Dinotefuran Ti Spinosad Dirtotefuran TI Abamectin Thiamethoxam Ti Spinosad -Thiamethoxam TI Abamectin Clothianidin TI Spinosad Clothianidin Ti Abamectin Nithiazine -TI Spinosad Nithiazine Ti Abamectin Flonicamid Tl Spinosad -Flonicaniid
II
TI Abamectin Fipronil TI Spinosad Fipronil TI Abamectin Pyrifluquin-Ti Spinosad Pyrifluquin- -______________ azone _________________ azone TI Abamectin Pymetrozine TI Spinosad Pymetrozine TI Abamectin Sulfoxaflor TI Spinosad Suifoxaflor Ti Abamectin Spirotetrarnat TI Spinosad Spirotetramat TI pinetoram hacloprid TI Chlorpyrifos Imidacloprid Ti Spinetoram Thiacloprid TI Chiorpyrifos Thiacprid TI Spinetorain Acetamiprid Ti Chiorpyrifos Acetamiprid TI pinetoram Nitenpyram TI Chiorpyrifos Nitenpyram Ti Spinetoram -Dinotefuran Ti Chiorpyrifos Dinotefuran TI Spinetoram Thiamethoxam TI Chiorpyrifos Thiainethoxam Ti Spinetoram Clothianidin TI Chiorpyrifos Clothianidin TI Spinetorain Nithiazine Ti Chiorpynfos Nithiazine Ti Spinetoram Flonicamid -TI Chiorpyrifos Flonicamid TI pinetoram Fipronil Ti Chiorpyrifos FiproniL TI Spinetoram Pyrifluquin-TI Chiorpyrifos Pyrifluquin- -_______________ azone -__________________ azone Ti Spinetoram Pymetrozine Ti Chiorpyrifos Pymetrozine TI Spinetoram Sulfoxaflor Ti Chiorpyrifos Sulfoxaflor TI Spinetorani Spirotetramat TI Chiorpyrifos Spirotetramat Ti Thiodicarb Imidacloprid Ti Chiorantraniliprole Imidacloprid Ti Thiodicarb Thiacloprid TI Chiorantraniliprole Thiacloprid Ti Thiodicarb Acetamiprid TI Chiorantraniliprole Acetamiprid Ti Thiodicarb Nitenpyram TI Chlorantraniliprole Nitenpyram TI Thiodicarb Dinotefuran TI Chiorantraniliprole Dinotefuran Ti Thiodicarb Thiamethoxam TI Chiorantraniliprole Thianiethoxain TI Thiodicarb Clothianidin TI Chiorantraniliprole Clotbianidin Ti Thiodicarb Nithiazine Ti Chiorantraniliprole Nithiazine I_ Thiodicarb Flonicamid Ti Chlorantraniliprole Flonicamid j'I_ Thiodicarb Fipronil TI ChIorantranipro1e Fipronil TI Thiodicarb Pynfluquin-Ti Chiorantraniliprole Pyrifluquin- -______________ azone _________________ azone TI Thiodicarb Pymetrozine Ti Chiorantrani liprole Pymetrozine TI Thiodicarb Sulfoxaflor -Ti Chiorantraniliprole Sulfoxaflor TI Thiodicarb Spirotetramat Ti Chlorantraniliprole Spirotetramat Ti Cyantraniliprole Imidacloprid Ti Bacillus firmus Imidacloprid TI Cyantranijprole Thiacloprid TI Bacillus firmus Thiacloprid TI Cyantraniliprole Acetaniiprid -TI Bacillus firmus Acetamiprid TI Cyantraniliprole Nitenpyram Ti Bacillus firmus Nitenpyram Ti Cyantraniliprole Dinotefuran Ti Bacillus firmus Dinotefuran TI Cyantraniliprole Thiamethoxam TI Bacillus firmus Thiamethoxam TI Cyantraniliprole Clothianidin TI Bacillus firmus Clothianidin TI Cyantraniliprole Nithiazine TI Bacillus firmus Nithiazine TI Cyantraniliprole Flonicamid TI Bacillus firmus Flonicamid TI çyantraniliprole Fipronil TI Bacillus firmus Fipronil Ti Cyantraniliprole Pynfiuquin-Ti Bacillus firmus yrif1uguin-azone _________________ azone TI Cyantraniliprole Pymetrozine TI Bacillus firmus Pymetrozine Ti Cyantraniliprole Sulfoxafior -TI Bacillus firmus Sulfoxaflor Ti Cyantraniliprole Spirotetramat TI Bacillus firmus Spirotetramat TI Bacillus subtilis_ Imidacloprid TI Pasteuria penetrans Imidacloprid TI Bacillus subtilis Thiacloprid TI Pasteuria penetrans Thiacloprid TI Bacillus subtilis -Acetamiprid TI Pasteuria penetrans Acetamiprid TI Bacillus subtilis Nitepyram TI Pasteuria penetrans Nitenpyram TI Bacillus subtilis Dinotefuran Ti Pasteuria penetrans Dinotefuran TI Bacillus subtilis Thiamethoxain TI Pasteuria penetrans Thiamethoxam TI Bacillus subtilis -Clothianidin -Ti Pasteuria penetrans Clothianidin TI Bacillus subtilis Nithiazine Ti Pasteuria penetrans Nithiazine Ti Bacillus subtilis Flonicamid Ti Pasteuria penetrans Flonicamid Ti Bacillus subtilis Fipronil TI Pasteuria penetrans Fipronil Ti Bacillus subtilis Pyrifluquin-Ti Pasteuria penetrans Pyrifluquin- ______________ azone _________________ azone Ti Bacillus subtilis Pymetrozine TI Pasteuria penetrans Pymetrozine TI Bacillus subtilis Sulfoxaflor -TI Pasteuria penetrans Sulfoxaflor TI Bacillus subtilis Spirotetramat -Ti Pasteuria penetrans Spirotetramat
AR C AB C
Ti Tefluthrin Sedaxane TI Lambda-cyhalothrin Sedaxane Ti Tefluthrin Fludioxonil -Ti Lambda-cyhalothrin Fludioxonil TI Tefluthrin Metalaxyl Ti Lambda-cyhalotbrin Metalaxyl Ti Tefluthrin Mefenoxam Ti Lambda-cyhalothrin Mefenoxam Ti Tefluthrin Cyprodinil Ti Lambda-cyhalothrin Cyprodinil Ti Tefluthrin Azoxystrobin Ti Lambda-cyhalothrin Azoxystrobin Ti Tefluthrin Tebuconazole Ti Lambda-cyhalothrin Tebuconazole TI Tefluthrin Difenoconazole Ti Lambda-cyhalothrin Difenoconazole TI Tefluthrin Thiabendazole Ti Lambda-cyhalothrin Thiabendazole TI Tefluthrin Fluopyram TI Lambda-cyhalothrin Fluopyrain Ti Tefluthrin Penflufen Ti Lambda-cyhalothrin Penflufen Ti Tefluthrin Fuxapyroxad Ti Lambda-cyhalothrin Fuxapyroxad TI Abamectin Sedaxane -Ti Spinosad Sedaxane Ti Abamectin Fludioxonil Ti Spinosad Fludioxonil Ti Abamectin Metalaxyl Ti Spinosad Metalaxyl TI Abamectin Mefenoxam Ti Spinosad Mefenoxam Ti Abamectin Cyprodinil Ti Spinosad çyprodinil TI Abamectin Azoxystrobin Ti Spinosad Azoxystrobin TI Abamectin Tebuconazote TI Spinosad Tebuconazole Ti Abamectin Difenoconazole Ti Spinosad Difenoconazole TI Abaniectin Thiabendazole Ti Spinosad -Thiabendazole TI Abamectin Fluopyram TI Spinosad Fluopyram TI Abamectin Penflufen TI Spinosad Penflufen Ti Abamectin Fuxapyroxad TI Spinosad Fuxapyroxad TI Spinetorani Sedaxane TI Chiorpyrifos Sedaxane TI!p1etoram -Fludioxonil TI Chiorpyrifos Fludioxonil Ti pnetoram -Metalaxyl TI -Chiorpyrifos Metalaxyl I Ti Spinetoram Mefenoxam TI Chiorpyrifos Mefenoxam -TI Spinetoram -Cyprodinil TI Chlorpyrifos -Cyprodinil TI Spnetoram -Azoxystrobifl. TI Chiorpyrifos -AzoxystrobiTi TI Spinetoram Tebuconazole TI Chlorpyrifos Tebuconazoic TI!p!netoram -DifenoconazOle TI Chlorpyrifos Difenoconazo]ç..
Ti Spinetoram Thiabendazole TI Chiorpyrifos Thiabendazole Ti Spinetoram -Fluopyram Ti Chiorpyrifos Fluopyram TI Spinetoram -Penflufen Ti Chlorpyrifos Penflufen Ti Spinetoram -Fuxapyroxad Ti Chiorpyrifos Fuxapyroxad TI Thiodicarb -Sedaxane Ti Chiorantraniliprole Sedaxane TI Thiodicarb Fludioxonil TI Chiorantraniliprole FludioxoniL Ti Thiodicarb -Metalaxyl TI Chlorantranilipro1_ Metalaxyl TI Thiodicarb Mefenoxam TI ChLorantraniliprole Mefenoxam Ti Thiodicarb -Cyprodinul TI Chiorantraniliprole Cyprodinil Ti Thiodicarb -Azoxystrobin TI Chiorantraniliprole Azoxystrobin TI Thiodicarb -Tebuconazole TI Chlorantraniliprole_ Tebuconazole TI Thiodicarb Difenoconazole TI Chlorantraniliprole_ Difenoconazole Ti Thiodicarl, Thiabendazole TI Chiorantraniliprok Thiabendazole TI Thiodicarb Fluopyram TI ChlorantranhliprOiç_ Fluopyram TI Thiodicarb -Penflufen TI Chlorantraniliprole Penflufen Ti Thiodicarb Fuxapyroxad Ti Chiorantraniliprole Fuxapyroxad TI Cyantraniliprole Sedaxane TI Bacillus firmus Sedaxane TI Cyantraniliprole Fludioxonil TI Bacillus firmus -Fludioxonil Ti Cyantraniliprole Metalaxyl Ti Bacillus firmus Metalaxyl TI *çyantraniliprole Mefenoxam TI Bacillus firmus Mefenoxam -TI Cyantraniliprole Cyprodinil TI Bacillus firmus prodini1 TI Cyantranilipro! Azoxystrobin Ti Bacillus firmus Azoxystrobin TI Cyantraniliprole Tebuconazole TI Bacillus flrmus Tebuconazole Ti CyantraniliproJ Difenoconazote TI Bacillus firmus Difenoconazole Ti Cyantraniliprole Thiabendazole TI Bacillus firmus Thiabendazole Ti Cyantraniliproi Fluopyram TI Bacillus firmus Fluopyram Ti Cyantraniliprole Penflufen TI Bacillus firmus -Penflufen TI Cyantraniliprole Fuxapyroxad -Ti Bacillus firmus jpyxa4.
TI Bacillus subtilis Sedaxane TI Pasteuria penetrans Sedaxane TI Bacillus subtilis Fludioxonil -TI Pasteuria penetrans FludioxqjL....
TI Bacillus subtilis Metalaxyl -TI Pasteuria penetrans Metalaxyl TI Bacillus subtilis Mefenoxam -TI Pasteuria penetrans Mefenoxam TI Bacillus subtilis çyprodinil -TI Pasteuria penetrans çyprodinil Ti Bacillus subtilis Azoxystrobin TI Pasteuria penetrans Azoxystrobin Ti Bacillus subtilis Tebuconazole -Ti Pasteuria penetrans Tebuconazole -TI Bacillus subtilis Difenoconazole TI Pasteuria penetrans Difenoconazole_ TI Bacillus subtilis Thiabendazole TI Pasteuria penetrans Thiabendazole TI Bacillus subtilis Flupyram -TI Pasteuria penetrans Fluopyram TI Bacillus subtilis Penflufen TI Pasteuria penetrans Penflufen - [TI I Bacillus subtilis I Fuxapyroxad _L I Ti I Pasteur a penetrans I Fuxapyroxad jj
AB C AB ______
TI Tefluthrin Lambda-TI Lambda-cyhalothrin Tefluthrin --cyhalothrin - Ti Tefluthrin Abaniectin -Ti Lambda-cyhalothrin Abamectin -TI Tefluthrin Spinosad TI Lambda-cyhalothrin Spinosad TI Tefluthrin Spinetorani TI Lambda-cyhalothrin Spinetoram TI Tefluthrin Chiorpyrifos Ti Lambda-cyhaiothrin Chiorpyrifos - TI Tefluthrin Thiodicarb Ti Lambda-cyhalothrin Thiodicarb - TI Tefluthrin Chiorantranhli-TI Lambda-cyhalothrin Chlorantranili- -________________ prole ____________________ prole TI Tefluthrin Cyantranili-Ti Lambda-cyhalothrin Cyantranili- _________________ prole --prole TI Tefluthrin Bacillus firmus TI Lambda-cyhaiothrin Bacillus firmus TI Tefluthrin Bacillus subtilis TI Lambda-cyhalothrin Bacillus subtilis TI Tefluthrin Pasteuria Ti Lambda-cyhalothrin Pasteuria -______________ penetrans jnetranS TI Abamectin Tefluthrin Ti Spinosad Tefluthrin TI Abamectin Lambda-Ti Spinosad Lambda- ______________ cyhalothrin --_________________ yha1othrin TI Abamectin Spinosad TI Spinosad Abamectin TI Abamectin Spinetoram TI Spinosad -Spinetoram TI Abamectin Chiorpyrifos TI Spinosad Chlorpyrifos Ti Abamectin Thiodicarb TI Spinosad Thiodicarb TI Abamectin Chiorantranili-TI Spinosad Chlorantranili- -________________ prole ___________________ poIe TI Abamectin Cyantranili-TI Spinosad Cyantranili- ________________ prole -___________________ prole TI Abamectin Bacillus firmus TI Spinosad Bacillus firmus Ti Abamectin Bacillus subtilis TI Spinosad Bacillus subtilis TI Abamectin Pasteuria Ti Spinosad Pasteuria ______________ penetrans _________________ penetrans Ti Spinetoram Tefluthrin Ti Chiorpyrifos Tefluthrin TI Spinetoram Lambda-Ti Chiorpyrifos Lambda- _______________ cyhaiothrin __________________ cyhalothrin Ti Spinetoram Abamectin Ti Chiorpyrifos -Abamectin Ti Spinetoram Spinosad Ti Ch1orpyjfos pinosad Ti Spinetoram Chiorpyrifos TI Chiorpyrifos Chlorantraniii- ______________ _____________ -_________________ p!ole TI Spinetoram Thiodicarb TI Chlorpyrifos Thiodicarb TI Spinetoram Chlorantranil i-Ti Chlorpyrifos Chiorantranili- _______________ prole -__________________ jo1e TI Spinetoram Cyantranili-TI Chiorpyrifos Cyantranili- -prole ___________________ prole TI inetoram Bacillus firmus Ti Chlorpyrifos Bacillus firmus Ti Spineloram Bacillus subtilis TI Chlorpyrifos Bacillus subtilis Ti Spinetoram Pasteuria] TI Chiorpyrifos Pasteuria I _______________ penetranS ptrans TI Thiodicarb Tefluthrin TI Chiorantraniliprole ffluthrin TI Thiodicarb Lambda-TI Chiorantraniliprole Lambda- -cyhalothnn -_________________ yalothrin TI Thiodicarb Abainectin TI Chiorantraniliprole Abamectin Ti Thiodicarb osa TI Chiorantraniliprole pinosad TI Thiodicarb Chiorantranili-TI Chiorantraniliprole Chiorantranili- --prole -____________ prole Ti Thiodicarb -Chiorpyrifos TI ChiorantraniliprOle Chiorpyrifos Ti Thiodicarb Chlorantranili-TI Chiorantraniliprole Thiodicarb -_prole - Ti Thiodicarb Cyantraniti-TI Chiorantraniliprole Cyantranili- ______________ prole _________________ pole TI Thiodicarb Bacillus firmus TI Chlorantraniliprole Bacillus firmus TI Thiodicarb -Bacillus subtiiis TI ChiorantranhliprOle Bacillus subtilis TI Thiodicarb Pasteuria TI ChiorantraniliprOle Pasteuria -_______________ penetraflS --enetranS TI Cyantraniliproç Tefluthrin TI Bacillus firmus Tefluthrin - Ti Cyantranhliprole Lambda-TI Bacillus firnius Lambda- ______________ cyhalothrin -_________________ yhalothrin - IL Cyantraniliproi Abamectin TI Bacillus firmus Abainectin -TI Cyantraniliproiç_ Spinosad TI Bacillus firmus Spinosad TI Cyantraniliprole Chiorantraflili-Ti Bacillus firmus Chlorantranili- -________________ prole pTole Ti CyantraniIipro! Chiorpyrifos Ti Bacillus firmus -Chlorpyrifos TI Cyantraniliprole Thiodicarb TI Bacillus firmus Thiodicarb TI Cyantraniliprole Chlorantranilipr Ti Bacillus firmus Chlorantraniii-ole _____________ prole TI Cyantraniliprole Bacillus firmus Ti Bacillus firmus Cyantranili----prole TI Cyantraniliprole Bacillus subtilis Ti Bacillus firmus Bacillus subtilis TI Cyantraniliprole Pasteuria Ti Bacillus firmus Pasteuria -_______________ penetraflS -___________________ penetranS TI Bacillus subtilis Tefluthnn 11 Pasteur a penetrans Ilefluthiin Ti Bacillus subtilis Lambda-Ti Pasteuria penetrans Lambda- ______________ yhaIothrin -________________ cyhalothrin Ti Bacillus subtilis Abamectin TI Pasleuria penetrans_ Abamectin TI Bacillus subtilis Spinosad -Ti Pasleuria penetrans Spinosad TI Bacillus subtilis Chlorantranili-TI Pasteuria penetrans Chiorantranili- -_______________ prole -prole TI Bacillus subtilis Chlorpyrifos -TI Pasteuria penetrans Chiorpyrifos TI Bacillus subtilis Thiodicarb TI Pasteuria penetrans Thiodicarb TI Bacillus subtilis Chlorantranili-TI Pasteuria penetrans Chiorantranili- -_________ prole -_ple TI Bacillus subtilis Cyantranili-TI Pasteuria penetrans Cyantranili- -______________ pole -prole TI Bacillus subtilis Bacillus firmus_ 1jj Pasteuria penetrans Bacillus firmus [TI Bacillus subtilis Pasteuria Pasteuria penetrans Bacillus subtilis -penetraflS ______ Aii -TI Imidacloprid Sedaxane Ti iiiiacloprid Sedaxane TI Imidacloprid Fludioxonit TI Thiacloprid Fludioxonil TI lmidacloprid Metalaxyl -TI Thiacloprid Metalaxyl TI lrnidacloprid Mefenoxani TI Thiacloprid Mefenoxam Ti Imidacloprid Cyprodinil TI Thiacloprid Cyprodinil Tt Imidacloprid Azoxystrobin -TI Thiacloprid Azoxystrobi Ti lmidacloprid Tebuconazole TI Thiacloprid Tebuconazole TI Imidacloprid Difenoconazole TI Thiacloprid Difenoconazole Ti imidacloprid Thiabendazole -TI Thiacloprid Thiabendazole Ti linidacloprid Fluopyram -TI Thiacloprid Fluopyram TI Imidacloprid -Penflufen TI Thiacloprid Penflufen Ti Imidacloprid -Fuxapyroxad Ti Thiacloprid Fuxapyroxad - TI Acetamiprid -Sedaxane __ TI Nitenpyram!edaxane - Ti Acetamiprid Fludioxonil TI Nitenpyram Fludioxonil -TI Acetamiprid Metalaxyl TI Niteipyram Metalaxyl Ti Acetamiprid Mefenoxam TI Nitenpyram Mefenoxani - Ti Acetamiprid Cyprodinil TI Nitenpyram Cyprodinil - TI Acetamiprid Azoxystrobin TI Nitenpyram Azoxystrobin -TI Acetamiprid Tebuconazole TI Nitenpyram -Tebuconazole TI Acetamiprid -DifenoconazoI TI Nitenpyram Ti Acetamiprid Thiabendazo1e TI Nitenpyrani -en4oI TI Acetamiprid Fluopyram TI Nitenpyram -Fluopyram - TI Acetamiprid Penflufen TI Nitenpyram Penflufen -TI Acetamiprid Fuxapyroxad TI Nitenpyram Fuxapyroxad TI Dinotefuran -Sedaxane -TI Thiamethoxam_ Sedaxane TI Dinotefuran -Fludioxonil Ti Thiamethoxam_ Fludioxonil TI Dinotefuran -Mctalaxyl TI Thiamethoxam_ Metalaxyl TI Dinotefuran Mefenoxam TI Thiamethoxam_ Mefenoxam Ti Dinotefuran çyprodinil TI Thianiethoxam çyprodinil TI Dinotefuran Azoxystrobin Ti Thiamethoxam Azoxystrobin Ti Dinotefuran Tebuconazole TI Thjainethoxam_ Tebuconazole TI Dinotefuran Difenoconazole TI Thiamethoxam_ Difenoconazote Ti Dinotefuran Thiabendazole TI Thiarnethoxam Thiabendazole TI Dinotefuran Fluopyrani Ti Thiamethoxam Fluopyram TI Dinotefuran Penflufen -TI Thiamethoxam Penflufen TI Dinotefuran Fuxapyroxad TI Thiamethoxam Fuxapyroxad Ti Clothianidin Sedaxane Ti Nithiazine -Sedaxane TI Clothianidin Fludjoxoflhl TI Nithiazine -Fludioxonil TI çlothianidin Metalaxyl Ti Nithiazine Metalaxyl Ti Clothianidin Mefenoxam TI Nithiazine Mefenoxam TI Clothianidin Cyprodinil -TI Nithiazine C rodinil TI Clothianidin Azoxystrobin TI Nithiazine Azox strobin Clothianidin _I TebuconazOIe hiazine -Tebuconazo1e TljClothianidin -Difenoconazoic Ti Nithiazine -Difenoconazo Clothianidin -Thiabendazole_ Ti Nithiazine -Thiabendazole flJ Clothianidin -Fluopyram Ti Nithiazine -Fluopyram jfl Clothianidin -Pentlufen TI Nithiazine -Penflufen Ti Clothianidin -Fuxapyroxad TI Nithiazine Fuxapyroxa(L 1T Flonicamid -Sedaxane Ti iproni1 axane TI Flonicamid Fludioxonil Ti pronil -Fludioxonil TI Flonicamid -Metalaxyl TI Fipronil -Metalaxyl TI Flonicamid -Mefenoxam Ti Fipronil -Mefenoxam Ti Flonicamid -Cyprodinil TI Fipronil -Cyprodinil Ti Flonicamid -Azoxystrobin TI Fipronhl -Azoxystrobin__ TI Flonicamid Tebuconazole Ti Fipronil Tebuconazole Ti iionicamid DifenoconazOle Ti jronii Difenoconazole Ti Flonicamid Thiabendazo!! TI Fipronil Thiabendazoic_ TI Flonicamid Fluopyram TI Fiproni) Fluopyram Ti Flonicamid -Penflufen TI Fipronhl Penflufen Ti Flonicamid Fuxapyroxad --TI Fipronil Fuxapyroxad TI yrifluguinaz2 Sedaxane -Ti Pymetrozifle Sedaxane Ti yrifluguinazo Fludioxonil --Ti Pymetrozine Fludioxonil__ TI yrifluguinazo Metalaxyl TI Pymetrozifle TI Pyrifluquinazone Mefenoxam TI Pymetrozifle Mefenoxam TI Pyrifluguinazo Cyprodinil = TI PymetroZifle yprodini1 Ti PyrifluguinazO Azoxystrobin -TI Pymetrozifle Azoxystrobin -Ti Pyrifluguinazc Tebuconazoic --TI Pymetrozifle Tebuconazole Ti Pyrif1uguinazO! pfenoconazole_ Ti Pymetrozine jfenoconazoIe_ TI Pyrifluguinazofle Thiabendazole --TI Pymetrozifle Thiabendazole -Ti PyrifluguinazOfl Fluopyram --TI Pymetrozifle TI PyrifluguinazO!ç Penflufen TI Pymetrozine Penflufen TI Pyrifluguinaz Fuxapyroxad --TI Pymetrozifle Fuxapyroxad -TI Sulfoxaflor Sedaxane -TI Spirotetramat Sedaxane TI Sulfoxaflor Fludioxonil --Ti SpirotetramaL Fludioxonil - TI Sulfoxaflor Metalaxyl TI SpirotetramaL Metalaxyl - TI Sulfoxaflor Mefenoxam --TI pirotetramat Mefenoxam - TI Sulfoxaflor çyprodinil -TI SpirotetramaL_ çyprodinil -TI Sulfoxaflor Azoxystrobifl --Ti SpirotetramaL_. Azoxystrobifl TI Sulfoxafior Tebuconazole -TI Spirotetramat Tebuconazole TI Sulfoxaflor Difenoconaz_ -TI potetramat -DifenoconaZole Ti Sulfoxaflor ThiabendaZOle_ -TI potetramat ThiabendaZole_ Ti Sulfoxaflor Fluopyram --TI!potetramat -Fluopyram -TI Sulfoxaflor Penflufen ________ TI Spirotetramat Penflufen Ti Sulfoxaflor Fuxapyroxad TI, Spirotetramat i Fuxapyroxad - [A1B C [A B C [Ti Imidactoprid Thiacloprid 1 [TI Thiacloprid Imidacioprid TI Imidacloprid Acetarniprid J LT1 Thiacloprid Acetamiprid TI Imidacloprid enpyrarn Ti Thiacloprid Nitenpyram TI lmidacloprid Dinotefuran Ti Thiactoprid Dinotefuran TI Imidacloprid Thiamethoxam Ti Thiacloprid Thiamethoxam TI Imidacloprid Clothianidin TI Thiacloprid Clothianidin TI Imidaclopnd Nithiazine Ti Thiacloprid Nithiazine TI Imidacloprid Flonicamid Ti Thiacloprid Flonicamid TI Imidacloprid Fipronil TI Thiacloprid FiproniL TI Imidacloprid Pyrifluquin-Ti Thiacloprid Pyrifluquin- ______________ azone ______________ azone TI Imidacioprid Pymetrozine TI Thiacloprid Pymetrozine Ti Imidacloprid Sulfoxaflor TI Thiacloprid Sulfoxaflor Ti Imidacloprid Spirotetramat Ti Thiacloprid Spirotetramat TI Acetamiprid imidacloprid TI Nitenpyram Imidacloprid Ti Acetamiprid Thiacloprid TI Nitenpyram Thiacloprid Ti Acetamiprid Nitenpyram TI Nitenpyram Acetamiprid Ti Acetamiprid Dinotefuran TI Nitenpyram Dinotefuran 1'l Acetamiprid Thiamethoxam Ti Nitenpyram Thianiethoxam TI Acetamiprid Clothianidin Ti Nitenpyram Clothianidin TI Acetaniiprid Nithiazine Ti Nitenpyram Nithiazine TI Acetamiprid Ftonicamid Ti Nitenpyram Flonicamid Ti Acetamiprid Fipronil TI Nitenpyrarn Fipronil TI Acetamiprid Pyrifluquin-Ti Nitenpyram Pyrifluquin- -______________ azone ______________ azone TI Acetamiprid Pymetrozine Ti Nitenpyram Pymetrozine TI Acetamiprid Sulfoxaflor TI Nitenpyram Sulfoxaflor Ti Acetamiprid Spirotetramat TI Nitenpyram Spirotetramat Ti Dinotefuran -Imidacloprid TI Thiamethoxarn lmidacloprid TI Dinotefuran Thiacloprid Ti Thiamethoxarn Thiacloprid TI Dinotefuran Acetamiprid Ti Thiainethoxam Acetamiprid Ti Dinotefuran Nitenpyram Ti Thiamethoxam Nitenpyram TI Dinotefuran Thiamethoxam TI Thiamethoxarn Dinotefuran Ti Dinotefuran Clothianidin TI Thiamethoxam Clothianidin TI Dinotefuran Nithiazine TI Thiamethoxam Nithiazine TI Dinotefuran Flonicamid TI Thiamethoxam Flonicamid TI Dinotefuran -Fipronil TI Thiamethoxam Fipronil TI Dinotefuran Pyrifluquin-TI Thiamethoxam Pyrifluquin- ______________ azone ______________ azone TI Dinotefuran Pymetrozine Ti Thiamethoxam Pymetrozine TI Dinotefuran Suifoxaflor Ti Thiamethoxam Sulfoxaflor TI Dinotefuran Spirotetramat TI Thiamethoxani Spirotetramat -Ti Clothianidin hnidacloprid TI Nithiazine Imidacloprid TI Clothianidin Thiacloprid TI Nithiazine Thiacloprid TI Clothianidin Acetamiprid TI Nithiazine Acetamiprid -TI Clothianidin Nitenpyram TI Nithiazine Nitenpyram TI Clothianidin Dinotefuran TI Nithiazine Dinotefuran -TI Clothianidin Thiamethoxam TI Nithiazine Thiamethoxam TI Clothianidin Nithiazine TI Nithiazine CLothianidin TI Clothianidin Flonicamid TI Nithiazine --Flonicamid TI Clothianidin Fipronil TI Nithiazine Fipronil TI Clothianidin Pyi-ifluquin-TI Nithiazine Pyrifluquin- ______________ azone ______________ azone TI Clothianidin Pymetrozine TI Nithiazine Pymetrozine -TI Clothianidin Sulfoxaflor Ti Nithiazine Sulfoxaflor Ti Clothianidin Spirotetramat TI Nithiazine pirotetramat Ti Flonicamid Imidacloprid Ti Fipronil Imidacloprid Ti Flonicamid Thiacloprid Ti Fipronil Thiacloprid TI Flonicamid Acetamiprid TI Fipronil Acetamipnd TI Flonicamid Nitenpyram Fipronil Nitenpyram TI Flonicamid Dinotefuran I Fipronil Dinotefuran TI Flonicamid Thiamethoxam I Fipronil Thiamethoxam TI Flonicamid Clothianidin I Fipronil Clothianidin TI Flonicamid Nithiazine I -Fipronil Nithiazine TI Flonicamid Fipronil T Fipronil Flonicamid TI Flonicamid Pyrifluquin-T Fipronil Pyrifluquin- ______________ azone -______________ azone TI Flonicamid Pynietrozine Ti Fipronil Pymetrozine TI Flonicamid Sulfoxaflor TI Fipronil Sulfoxaflor TI Flonicamid Spirotetramat Ti Fipronil Spirotetramat TI Pyrifluguinazone Imidacloprid Ti Pymetrozine Imidacloprid TI Pyrifluguinazone Thiacloprid -Ti Pymetrozine Thiac1oprid TI Pyrifluguinazone Acetamiprid Ti Pymetrozine Acetamiprid TI Pyrifluguinazone Nitenpyram TI Pyrnetrozine Nitenpyram TI Pyrifluguinazone Dinotefuran TI jetrozine Dinotefuran TI Pyrifluquinazone Thiamethoxam TI Pymetrozine Thiamethoxam TI Pyrifluguinazone Clothianidin TI Pymetrozine Clothianidin TI Pyrifluquinazone Nithiazine TI Pymetrozine Nithiazine TI 4fluguinazone Flonicamid Ti Pymetrozine Flonicamid Ti Pyrifluguinazone Fipronil Ti Pymetrozine Fipronil TI Pyrifluquinazone Pymetrozine Ti Pymetrozine Pyrifluquin- _______________ _______________ _______________ azone TI Pyrifluguinazone Sulfoxaflor Ti Pymetrozine Sulfoxaflor Ti Pyrifluquinazone Spirotetramat TI Pymetrozine Spirotetramat TI Sulfoxaflor Imidactoprid = TI Spirotetramat Imidacloprid TI Sulfoxaflor Thiacloprid TI Spirotetramat Thiacloprid T Sulfoxaflor Acetamiprid TI piroteIramat Acetamiprid T Sulfoxaflor Nitenpyram -TI Spirotetramat Nitenpyram TI Sulfoxaflor Dinotefuran -Ti pirotetramat Dinotefuran TI Sulfoxaflor Thiamethoxam Ti Spirotetramat Thiamethoxam TI Sulfoxaflor Clothianidin TI Spirotetrarnat Clothianidin TI Sulfoxaflor Nithiazine TI Spirotetramat Nithiazine TI Sulfoxaflor Flonicamid TI Spirotetramat Flonicamid TI Sulfoxaflor Fipronil TI Spirotetrarnat Fipronil TI Sulfoxaflor Pyrifluquin-Ti Spirotetramat Pyrifluquin- ______________ azone -______________ azone Ti Sulfoxaflor Pymetrozine IL Spirotetramat Pymetrozine Ti Sulfoxaflor Spirotetramat TI Spirotetramat Sulfoxaflor "Ti" means a compound selected from Table 1.. A, B, C refer to components A, B and C. The present invention also relates to a method of controlling phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a combination of components A, B and C, e.g. when component C is a fungicide; a method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, to a plant susceptible to attack by a pest, or to plant propagation material susceptible to attack by a pest a combination of components A, B and C; a seed comprising a pesticidal mixture of components A, B and C; a method comprising applying to a seed, e.g. coating, a mixture of components A, B and C. The present invention also includes pesticidal mixtures comprising a component A, B and C in a synergistically effective amount; agricultural compositions comprising a mixture of component A, B and C in a synergistically effective amount; the use of a mixture of component A, B and C in a synergisticallyeffective amount for combating animal pests; the use of a mixture of component A, B and C in a synergistically effective amount for combating phytopathogenic fungi, e.g. when component C is a fungicide; a method of combating,animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a mixture of component A, B and C in a synergistically effective amount; a method for protecting crops from attack or infestation by animal pests and/or phythopathogenic fungi, which comprises contacting a crop with a mixture of component A, B and C in a synergistically effective amount; a method for the protection of seeds from soil insects and of the seedlings' roots and shoots from soil and foliar insects and/or phythopathogenic fungi comprising contacting the seeds before sowing and/or after pre-germination with a mixture of component A, B and C in a synergistically effective amount; seeds comprising, e.g. coated with, a mixture of component A, B and C in a synergistically effective amount; a method comprising applying to a seed, e.g. coating, a mixture of component A, B and C in a synergistically effective amount; a method of controlling phytopaihogenic, e.g. fungal, diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a combination of components A, B and C in a synergistically effective amount, e.g. when component C is a fungicide. In such applications the mixtures of A, B and C will normally be applied in a fungicidally effective amount. The invention also provides a method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, to a plant susceptible to attack by a pest, or to plant propagation material susceptible to attack by a pest, a combination of components A, B and C in a synergistically effective amount. In such applications mixtures of A, B and C O will normally be applied in an insecticidally, acaricidally, nematicidally or molluscicidally effective amount. In application components A, 13 and C may be applied simultaneously or separately.
The active ingredient combinations arc effective against harmful microorganisms, such as microorganisms, that cause phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria, e.g. when component C is a fungicide. The active ingredient combinations are effective especially against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerel [a, Uncinula); Basidiomycetes (e.g. the genus I-Iemileia, Rhizoctonia, Phakopsora, Puccinia,, Ustilago, Tilletia); Fungi imperfecti (also known as Deuteromycetes; e.g. Botrytis, Helminthosporiuin, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella); Oomycetes (e.g. Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudoscierospora, Plasmopara).
The mixtures of the present invention can be used to control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as animal pests. The animal pests which maybe controlled by the use of the invention compounds include those animal pests associated with agriculture (which term includes the growing of crops for food and fiber products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies). The mixtures of the invention are particularly effective against insects, acarines and/or nematodes.
According to the invention "useful plants" typically comprise the following species of plants: grape vines; cereals, such as wheat, barley, rye or oats; beet, such as sugar beet or fodder beet; fruits, such as pornes, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as marrows, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; Iauraceae, such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee; sugar cane; tea; vines; hops; durian; bananas; natural rubber plants; turf or omamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers. This list does not represent any limitation.
The term "useful plants' is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikirnate-3-phosphate-synthase) inhibitors, (IS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate-and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, 1-lerculex I® and LibertyLink®.
The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as ö-endotoxins, e.g. CrylA(b), CrylA(c), CryIF, CryIF(a2), CryIIA(b), CrylIlA, CryHlB(bl) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIPI, VIP2, VIP3 orVIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xeriorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3 -hydroxysteroidoxidase, ecdysteroid- UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, l-IMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
In the context of the present invention there are to be understood by 8-endotoxins, for example CryIA(b), CrylA(c), CryIF, CryIF(a2), CryllA(b), CryillA, CryllIB(bl) or Czy9c, or vegetative insecticidal proteins (VIP), for example VIP 1, VIP2, VIP3 or V1P3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). An example for a truncated toxin is a truncated CiyIA(b), which is expressed in the Btl 1 maize from Syngenta Seed SAS, as described below. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylIlAO55, a cathepsin-D-recognitiofl sequence is inserted into a CrylliA toxin (see WO 03/018810) Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EPA-0 427 529, EP-A-45 1 878 and WO 03/052073.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-O 367 474, EP-A-O 401 979 and WO 90/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any laxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available.
Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylIIB(bl) toxin); YieldGard Plus® (maize variety that expresses a CryIA(b) and a CryllIB(bI) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CryIA(c) toxin); Boilgard I® (cotton variety that expresses a CryIA(c) toxin); Boligard Il® (cotton variety that expresses a CryIA(c) and a CryIIA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CryillA toxin); NatureGard® and Protecta®.
Further examples of such transgenic crops are: 1. BtI I Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-3 1 790 St. Sauveur, France, registration number C/FR/96/05/l 0. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Osirinia nub i/a/is and Sesarnia nonagrioldes) by transgenic expression of a truncated CrylA(b) toxin. Bill maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'l-Iobit 27, F-3 1 790 St. Sauveur, France, registration number CIFR/96105110. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nub i/a/is and Sesamia nonagrioides) by transgenic expression of a CryIA(b) toxin. Btl 76 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
3. M1R604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR196/05f 10. Maize which has been rendered insect-resistant by transgenic expression of a modified CrylIlA toxin. This toxin is Cry3AO55 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a CrylIIB(bI) toxin and has resistance to certain Coleoptera insects.
5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, 13-1150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number CINL/00/1 0. Genetically modified maize for the expression of the protein CryiF for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02JM3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacieriurn sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thuringiensis subsp. kursiaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
Transgenic crops of insect-resistant plants are also described in BATS (Zentrum für Biosicherheil und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 I3asel, Switzerland) Report 2003, (jp:Ifbats.ch).
The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-O 392 225, WO 95/33818, and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. -Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KPI, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95133818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resist-ance genes", as described in WO 03/000906).
Useful plants of elevated interest in connection with present invention are cereals; soybean; rice; oil seed rape; pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vines and vegetables, such as tomatoes, potatoes, cucurbits and lettuce.
The term "locus" of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.
The term "plant propagation material" is understood to denote generative parts of a plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and paris of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds.
A further aspect of the instant invention is a method of protecting natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms against attack of fungi and/or animal pests, which comprises applying to said natural substances of plant and/or animal origin or their processed forms a combination of components A, 13 and C in a synergistically effective amount.
Accord ing to the instant invention, the term "natural substances of plant origin, which have been taken from the natural life cycle" denotes plants or parts thereof which have been harvested from the natural life cycle and which are in the freshly harvested form.
Examples of such natural substances of plant origin are stalks, leafs, tubers, seeds, fruits or grains. According to the instant invention, the term "processed form of a natural substance of plant origin" is understood to denote a form of a natural substance of plant origin that is the result of a modification process. Such modification processes can be used to transform the natural substance of plant origin in a more storable form of such a substance (a storage good). Examples of such modification processes are pre-drying, moistening, crushing, comminuting, grounding, compressing or roasting. Also falling under the definition of a processed form of a natural substance of plant origin is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.
According to the instant invention, the term "natural substances of animal origin, which have been taken from the natural life cycle and/or their processed forms" is understood to denote material of animal origin such as skin, hides, leather, furs, hairs and the like.
The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mould, e.g. when component C is a fungicide.
A preferred embodiment is a method of protecting natural substances of plant origin, which have been taken from the natural life cycle, and/or their processed forms against attack of fungi and/or animal pests, which comprises applying to said natural substances of plant and/or animal origin or their processed forms a combination of components A, B and C in a synergistically effective amount.
A further preferred embodiment is a method of protecting fruits, preferably pomes, stone fruits, soft fruits and citrus fruits, which have been taken from the natural life cycle, and/or their processed forms, which comprises applying to said fruits and/or their processed forms a combination of components A, B and C in a synergistically effective amount.
The combinations of the present invention may also be used in the field of protecting industrial material against attack of fungi, e.g. when component C is a fungicide.
According to the instant invention, the term "industrial material" denotes non-living materials which have been prepared for use in industry. For example, industrial materials which are intended to be protected against attack of fungi can be glues, sizes, paper, board, textiles, carpets, leather, wood, constructions, paints, plastic articles, cooling lubricants, aquaeous hydraulic fluids and other materials which can be infested with, or decomposed by, microorganisms. Cooling arid heating systems, ventilation and air conditioning systems and parts of production plants, for example cooling-water circuits, which may be impaired by multiplication of microorganisms may also be mentioned from amongst the materials to be protected. The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold.
The combinations of the present invention may also be used in the field of protecting technical material against attack of fungi, e.g. when component C is a fungicide.
According to the instant invention, the term "technical material" includes paper; carpets; constructions; cooling and heating systems; ventilation and air conditioning systems and the like. The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold.
The combinations according to the present invention, e.g. when component C is a fungicide, are particularly effective against powdery mildews; rusts; leafspot species; early blights and molds; especially against Septoria, Puccinia, Erysiphe, Pyrenophora and Tapesia in cereals; Phakopsora in soybeans; Hemileia in coffee; Phragmidium in roses; Alternaria in potatoes, tomatoes and cucurbits; Sclerotinia in turf, vegetables, sunflower and oil seed rape; black rot, red fire, powdery mildew, grey mold and dead arm disease in vine; Botrytis cinerea in fruits; Monilinia spp. in fruits and Penicillium spp. in fruits.
The combinations according to the present invention, e.g. when component C is a fungicide, are furthermore particularly effective against seedbome and soilborne diseases, such as Altemaria spp., Ascochyta spp., Botrytis cinerea, Cercospora spp., Claviceps purpurea, Cochliobolus sativus, Colletotrichum spp., Epicoccum spp., S Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusarium proliferatum, Fusarium solani, Fusariurn subglutinans, Gãumannomyces graminis, 1-lelminthosporium spp., Microdochium nivale, Phoma spp., Pyrenophora graminea, Pyricularia oryzac, Rhizoctonia solani, Rhizoctonia cerealis, Sclerotinia spp., Septoria spp., Sphacelotheca reilliana, Tilletia spp., Typhula incarnata, Urocystis occulta, Ustilago spp. or Verticillium spp.; in particular against pathogens of cereals, such as wheat, barley, rye or oats; maize; rice; cotton; soybean; turf; sugarbeet; oiJ seed rape; potatoes; pulse crops, such as peas, lentils or chickpea; and sunflower. The combinations according to the present invention, e.g. when component C is a fungicide, are furthermore particularly effective against post harvest diseasese such as Botrytis cinerea, Colletotrichum musae, IS Curvularia lunata, Fusarium semitecum, (ieotrichum candidum, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, Mucor piriformis, Penicilium italicurn, Penicilium solitum, Penicillium digitatum or Penicillium expansum in particular against pathogens of fruits, such as pomefruits, for example apples and pears, stone fruits, for example peaches and plums, citrus, melons, papaya, kiwi, mango, berries, for example strawberries, avocados, pomegranates and bananas, and nuts.
The combinations according to the invention, e.g. when component C is a fungicide, are particularly useful for controlling the following plant diseases: Altemaria species in fruit arid vegetables, Ascochyta species in pulse crops, Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes, Cercospora arachidicola in peanuts, Cochliobolus sati vus in cereals, Colletotrichum species in pulse crops, Erysiphe species in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Fusarium species in cereals and maize, Gäumannomyces graminis in cereals and lawns, Helminihosporium species in maize, rice and potatoes, Hemileia vastatrix on coffee, Microdochium species in wheat and rye, Phakopsora species in soybean, Puccinia species in cereals, broadleaf crops and perrenial plants, Pseudocercosporella species in cereals, Phragmidium mucronatum in roses, Podosphaera species in fruits, Pyrenophora species in barley, Pyricularia oryzae in rice, Rarnularia collo-cygni in barley, Rhizoctonia species in cotton, soybean, cereals, maize, potatoes, rice and lawns, Rhynchosporium secalis in barley and rye, Sclerotinia species in lawns, lettuce, vegetables and oil seed rape, Septoria species in cereals, soybean and vegetables, IS Sphacelotheca reilhiana in maize, Tilletia species in cereals, Uncinula necator, Guignardia bidwellii and Phomopsis viticola in vines, Urocystis occulta in rye, Ustilago species in cereals and maize, Venturia species in fruits, Monilinia species on fruits, Penicillium species on citrus and apples.
The combinations according to the present invention are furthermore particularly effective against the following animal pests: Myzuspersicae (aphid), Aphis gossypii (aphid), Aphisfabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvala lwgens (planthopper), Nep/:oeuixc incliceps (leafhopper), Nezara spp. (stinkbugs), Euschisius spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Franidiniella occidenialis (thrip), Thrips spp. (thrips), Leplinolarsa dece,nlineaia (Colorado potato beetle), A nihonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp.
(white flies), Bemisia labaci (white fly), Osirinia nubilalis (European corn borer), Spodopiera litioralis (cotton Ieafworm), Helioihis virescens (tobacco budworm), flelicoverpa arrnigera (cotton bohiworm), h'elicoverpa zea (cotton bohiworm), Sylepia derogata (cotton leaf roller), Pieris brassicac (white butterfly), Pluiella xy/oslella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), LocustajnigralOria (locust), Chorlioceles ierminfera (locust), Diabrolica spp.
(rootworms), Panonychus ulmi (European red mite), Panonychus din (citrus red mite), Teiranychus uriicae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllocopirula oleivora (citrus rust mite), Polyphagotarsonemus lotus (broad mite), Brevipalpu.c spp. (flat mites), Boophilus microplus (cattle tick), Dermacenior vaniabilis (American dog tick), Cienocephalides fells (cat flea), Lirionzyza spp.
(leafininer), Musca domeslica (housefly), Aedes aegypti (mosquito), Anopheles spp.
(mosquitoes), Culex spp. (mosquitoes)1 Lucillia spp. (blowflies), Blatiella germanica (cockroach), Periplanela americana (cockroach), Blalta onientalis (cockroach), termites of the Mastotermitidae (for example Masiolermes spp.), the Kalotermitidae (for example Neotermes spp.), the Rhinotermitidae (for example Cop: otermes formosanus, Reticulitermesfiavipes, R. speralu, R. virginicus, R. hesperus, and R. sanlonensis) and the Termitidae (for example Globitermes sulfureus), Solenopsis geminala (tire ant), IS Monomoniuin pharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp(citrus nematodes), !-laemonchus coniorlus (barber pole worm), Caenorhabdilis elegans(vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug).
The amount of a combination of the invention to be applied, will depend on various factors, such as the compounds employed; the subject of the treatment, such as, for example plants, soil or seeds; the type of treatment, such as, for example spraying, dusting or seed dressing; the purpose of the treatment, such as, for example prophylactic or therapeutic; the type of fungi and/or animal pest to be controlled or the application time.
The mixtures comprising a compound of formula I, e.g. those selected from table 1, and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, Le. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula 1 selected from Table I and the active ingredients as described above is not essential for working the present invention.
Synergistic activity is present when the fungicidal and/or animal pesticidal activity of the composition of A + B + C is greater than the sum of the fungicidal and/or pesticidal activities of A, B and C, and/or A and (B + C), and/or (A + B) and C, and br (A + C) and B. The method of the invention comprises applying to the useful plants, the locus thereof or propagation material thereof in admixture or separately, a synergistically effective aggregate amount of a component A, B and C. Some of said combinations according to the invention have a systemic action and can be used as foliar, soil and seed treatment pesticides.
With the combinations according to the invention it is possible to inhibit or destroy the phytopathogenic microorganisms and/or animal pests which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms and/or animal pests.
The combinations of the present invention are of particular interest for controlling a large number of fungi and/or animal pests in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.
The combinations according to the invention are applied by treating the fungi and/or animal pests, the useful plants, the locus thereof, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials threatened by fungus and/or animal pests, attack with a combination of components A, B and C in a synergistically effective amount.
The combinations according to the invention may be applied before or after infection or contaniination of the useful plants, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials by the fungi and/or animal pests.
When applied to the useful plants the compound of formula I is applied at a rate of 1 to 500 g aiiha in association with I to 5000 g a.i.Iha, particularly I to 2000 g a.i./ha, of a compound of each of components B and C, depending on the class of chemical employed as components B and C. Generally for plant propagation material, such as seed treatment, application rates can vary from 0.001 to I Og I kg of seeds of active ingredients for compounds of formula I. When the combinations of the present invention are used for treating seed, rates of 0.001 to 5 g of a compound of formula I per kg of seed, preferably from 0.01 to Ig per kg of seed, and 0.001 to 5 g each of a compound of component B arid C per kg of seed, preferably from 0.01 to 1 g per kg of seed are generally sufficient. When component C is a fungicide 0.001 to 50 g per kg of seed, preferably from 0.01 to 10 g per kg of seed, are generally sufficient.
The weight ratio of A to B and A to C may generally be between 1000: 1 and I: 1000.
In other embodiments that weight ratio of A to B may be between 500: I to 1: 500, for example between 100: 1 to 1: 100, for example between I: 50 to 50: 1, for example 1: 20 to 20: 1. In other embodiments that weight ratio of A to C may be between 500: I to 1: 500, for example between 100: 1 to 1: 100, for example between 1: 50 to 50: 1, for example I: 20 to 20: 1. In other embodiments that weight ratio of B to C may be between 500: I to 1: 500, for example between 100: I to 1: 100, for example between I:50to50: 1,forexamplel:20to20: 1.
lii cases where component C is component Cl and component C2, the above rates and ratios apply separately to Cl and C2.
The invention also provides pesticidal mixtures comprising a combination of components A, B and C as mentioned above e.g. in a synergistically effective amount, together with an agriculturally acceptable carrier, and optionally a surfactant.
The compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concen-trate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended.
Particularly formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin suiphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatly alcohol.
A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules. A typical a tank-mix formulation for seed treatment application comprises 0.25 to 80%, especially I to 75 %, of the desired ingredients, and 99.75 to 20 %, especially 99 1025 %, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 40 %, especially 0.5 to 30 %, based on the tank-mix formulation. A typical pre-mix formulation for seed treatment application comprises 0.5 to 99.9 %, especially ito 95 %, of the desired ingrcdients, and 99.5 to 0.1 %, especially 99 to 5 %, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 %, especially 0.5 to 40 %, based on the pre-mix formulation.
In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula I together with a compound of component B, and optionally other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components.
The action to be expected £ for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (COLBY, S.R. Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pages 20-22; 1967):.
ppm milligrams of active ingredient ( a.i.) per liter of spray mixture X = % action by active ingredient A) using p ppm of active ingredient Y % action by active ingredient B) using q ppm of active ingredient.
According to COLBY, the expected (additive) action of active ingredients A)+B) using p+q ppm of active ingredient is E = X + Y -____ If the action actually observed (0) is &eater than the expected action (13), then the action of the combination is super-additive, i.e. there is a synergistic effect. In mathematical S terms the synergism factor SF corresponds to OlE. In the agricultural practice an SF of? 1.2 indicates significant improvement over the purely complementary addition of activities (expected activity), while an SF of 0.9 in the practical application routine signals a loss of activity compared to the expected activity.

Claims (18)

  1. Claims 1. A pesticidal mixture comprising a component A, a component B and a component C, wherein component A is an enantiomeric mixture of a compound of formula I that is S enantiomerically enriched for the S enantiomerKJYLIAwherein the symbol * indicates the chiral centre; A' and A2 are C-H, or one of A' and A2 is C-H and the other is N; R' is a group selected from P1 to P11 CCF3 P1 0 P2 P3 P4 P5,,. P6 y0 LCF3 P10 P11 R2 is chiorodifluoromethyl or tn fluoromethyl; R3 is 3,5-dibromo-phenyl, 3,5-dichloro-phenyl, 3,4-dichloro-phenyl, 3,5-dichloro-4-fluoro-phenyl or 3,45-trichioro-phenYl; R4 is hydrogen, methyl or cyano; R5 is hydrogen; S or R4 and R5 together form a bridging 1,3-butadiene group; component B is a compound selected from Tefluthrin, Lainbda-cyhalothrin, Abamectin, Spinosad, Spinetoram, Chiorpyrifos, Thiodicarb, Chiorantraniliprole, Cyantraniliprole, Bacillus firmus, Bacillus subtilis, Pasteuria penetrans, Imidacloprid, Thiacloprid, Acetamiprid, Nitenpyram, Dinotefliran, Thiamethoxam, Clothianidin, Nithiazine, Flonicamid, Fipronil, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat; and component C is a compound selected from an insecticide, a fungicide and a nematicide, which insecticide is selected from neonicotinoids, carbamates, diamides, spinosyns, is phenylpyrazoles, pyrethroids, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat; which flingicide is selected from Azoxystrobin, Trifloxystrobin, Fluoxastrobin, Cyproconazole, Difenoconazole, Prothioconazole, Tebuconazole, Triticonazole, Fludioxonil, Ipconazole, Cyprodinil, Myclobutanil, Metalaxyl, Mefenoxam, Sedaxane, Thiobendazole, Fluopyram, Penflufen, Fuxapyroxad, Fluopyram, and Penthiopyrad; which nematicide is selected from abamectin, carbamate neniaticides organophosphorus nematicides, Captan, Thiophanate-methyl, Thiabendazole a compound of formula X,N(\>-s' s F Fx wherein n iS 0, 1 or 2 and the thiazole ring may be optionally substituted, Bacillus firmus, Bacillus cereus, Bacillus subtilis, and Pasteuria perietrans; wherein components B and C are different.
  2. 2. A pesticidal mixture according to claim 1, wherein A' and A2 are C-Fl.
  3. 3. A pesticidal mixture according to claim 1, wherein component A is an enainiomeric mixture of a compound selected from compound I to II that is enantiomerically enriched for the S enantiomer CI (Ia) wherein the symbol * indicates the location of the chiral centre; No. Ri R2 1 Me 2 Me HN'CFH :: Me 6 M 8 Mc :: yNyO
    11 Me iLCF3
  4. 4. A pesticidal mixture according to any one of claims I to 3, wherein component A is at least 80% enantiomerically enriched for the S enantiomer.
  5. 5. A pesticidal mixture according to any one of claims I to 3, wherein component A is at least 90% enantiomerically enriched for the S enantiomer.
  6. 6. A pesticidal mixture according to any one of claims I to 5, wherein component C is a compound selected from Thiamethoxam, Clothianidin, Nithiazine, Flonicamid, imidacloprid, Acetamipnd, Dinotefuran, Nitenpyram, Thiacloprid, Thiodicarb, Aldicarb, Carbofuran, Furadan, Fenoxycarb, Carbaryl, Sevin, Ethienocarb, Fenobucarb, Chiorantraniliprole, Cyantrani liprole, Flubendiamide, Spinosad, Spinetoram, Cyhalothri n, Larnbda-cyhalothrin, Gamma-cyhalothrin, Tefluthrin, Fiproni 1, Azoxystrobin, Trifloxystrobin, Fl uoxastrobin, Cyproconazole, Difenoconazole, Prothioconazole, Tebuconazole, Triticonazole, Fludioxoni I, Thiabendazole, Ipconazole, Cyprodini 1, Myclobutanil, Metalaxyl, Mefenoxam, Sedaxane, Fl uopyram, Periflufen, Fu.xapyroxad, Abamectin, Aldicarb, Thiodicarb, Carbofuran, Carbosulfan, Oxaniyl, Aldoxycarb, Ethoprop, Methomyl, Benomyl, Alanycarb, Iprodione, Phenamiphos, Fensulfothion, Terbufos, Fosthiazate, Dimethoate, Phosphocarb, Dichiofenthion, Isamidofos, Fosthietan, Isazofos, Ethoprophos, Cadusafos, Terbufos, Chlorpyrifos, Dichlofenthion, Heterophos, Isamidofos, Mecarphon, Phorate, Thionazin, Triazophos, S Diamidafos, Fosthietan, Phosphamidon, Imicyafos, Captan, Thiophanate-methyl, Thiabendazole, a compound of formula X, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetrainat, Bacillus firmus, Bacillus subtilis and Pasteuna penetrans.
  7. 7. A pesticidal mixture according to any one of claims I to 5, wherein component C is a compound selected from Tefluthrin, Lambda-cyhalothnn, Abamectin, Spinosad, Spinetoram, Chlorpyrifos, Thiodicarb, Chiorantraniliprole, Cyantranil iprole, Bacillus firmus, Bacillus subtilis, Pasteuria penetrans, Imidacloprid, Thiacloprid, Acetamiprid, Nitenpyram, Dinotefuran, Thiamethoxam, Clothianidin, Nithiazine, Flonicamid, Fipronil, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetrainat, wherein components B and C are different.
  8. 8. A pesticidal mixture according to any one of claims I to 5, wherein component B is a compound selected from Tefluthrin, Lambda-cyhalothrin, Abamectin, Spinosad, Spinetoram, Chiorpyrifos, Thiodicarb, Chlorantraniliprole, Cyantraniliprole, Bacillus firmus, Bacillus subtilis and Pasteuria penetrans; and component C is a compound selected from Imidacloprid, Thiacloprid, Acetamiprid, Nitenpyram, Dinotefuran, Thiamethoxam, Clothianidin, Nithiazine, Flonicamid, Fipronil, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetraniat.
  9. 9. A pesticidal mixture according to any one of claims I to 5, wherein component B is a compound selected from Tefluthrin, Lambda-cyhalothrin, Abamectin, Spinosad, Spinetoram, Chiorpyrifos, Thiodicarb, Chiorantraniliprole, Cyantraniliprole, Bacillus firmus, Bacillus subtilis and Pasteuria penetrans; and component C is a compound selected from Sedaxane, Fludioxonil, Metalaxyl, Mefenoxam, Cyprodinil, Azoxystrobin, Tebuconazole, Difenoconazole, Thiabendazole, Fluopyram, Penflufen and Fuxapyroxad.
  10. 10. A pesticidal mixture according to any one of claims I to 5, wherein component B is a compound selected from Imidacloprid, Thiacloprid, Acetarniprid, Nitenpyram, Dinotefuran, Thiamethoxam, Clothianidin, Nithiazme, Flonicamid, Fiproni I, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat; and component C is a compound selected from Sedaxane, Fludioxonil, Metalaxyl, Mefenoxam, Cyprodinil, Azoxystrobin, Tebuconazole, Difenoconazole, Thiabendazole, Fluopyram, Penfluferi and Fuxapyroxad.
  11. 11. A pesticidal mixture according to any one of claims I to 5, wherein component B is a compound selected from Tefluthrin, Lambda-cyhalothrin, Abamectin, Spinosad, Spinetoram, Chiorpyrifos, Thiodicarb, Chlorantraniliprole, Cyantraniliprole, Bacillus firmus, BacilLus subtilis and Pasteuria penetrans; and wherein the mixture comprises as component C, component Cl and component C2, wherein component CI is a compound selected from Imidacloprid, Thiacloprid, Acetamiprid, Nitenpyram, Dinotefluran, Thiamethoxam, Clothianidin, Nithiazine, Flonicarnid, Fipronil, Pyrifluquinazone, Pymetrozine, Sulfoxaflor and Spirotetramat; and component C2 is a compound selected from Sedaxane, Fludioxonil, Metalaxyl, Mefenoxam, Cyprodinil, Azoxystrobin, Tebuconazole, Difenoconazole, Thiabendazole, Fluopyram, Penflufen and Fuxapyroxad.
  12. 12. A pesticidal mixture according to any one of claims I to 11, wherein the mixture comprises an agricultural acceptable carrier and optionally a surfactant.
  13. 13. A pesticidal mixture according to any one of claims I to 12, wherein the weight ratio of A to each of components B and C is 1000:1 to 1:1000.
  14. 14. A pesticidal mixture according to any one of claims I to 13, wherein the mixture is not one comprising Cyantraniliprole and Thiamethoxam; or Chiorantraniliprole and Thiamethoxam.
  15. 15. A method of controlling phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a combination of components A, B and C, wherein components A, B and C are as defined in any one of claims I to 14.
  16. 16. A method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, to a plant susceptible to attack by a pest, or to plant propagation material susceptible to attack by a pest, a combination of components A, B and C, wherein components A, B and C are as defined in any one of claims Ito 14.
  17. 17. A seed comprising a pesticidal mixture as defined in any one of claims I to 14.
  18. 18. A method comprising applying to a seed a mixture as defined in any one of claims ito 14.
GB1109466.1A 2010-06-09 2011-06-06 Pesticidal mixtures comprising enantiomerically enriched isoxazoline derivatives Withdrawn GB2481118A (en)

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