Pesticide mixtures including isoxazoline derivatives, method of controlling insects, mites, nematodes or mollusks, and seed comprising said mixtures.
A synergistic mixture of isoxazoline compounds and other pesticides addresses the challenge of ineffective pest control at low doses by enhancing efficacy and safety, offering broader pest control and improved plant characteristics.
Patent Information
- Application Number
- BR122019019863
- Authority / Receiving Office
- BR · BR
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2011-05-31
- Filing Date
- 2012-05-30
- Publication Date
- 2026-07-28
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Existing pesticide formulations face challenges in achieving effective pest control, particularly against resistant strains, with individual components becoming ineffective at low application rates and requiring high doses, which can lead to safety and environmental concerns.
A synergistic mixture of compounds, including isoxazoline compounds and other pesticides, enhances pest control efficacy by reducing application rates while maintaining or improving effectiveness, broadening the spectrum of pest control, and offering additional benefits such as improved stability and safety.
The mixture achieves a synergistic effect, providing enhanced pest control even at reduced doses, broadening the spectrum of effectiveness, and improving stability and safety, with benefits including reduced application rates, increased safety, and improved plant characteristics.
Description
[001] The present invention relates to mixtures of active ingredients in pesticide terms and to methods of using the mixtures in the field of agriculture.
[002] EP1731512 discloses that certain isoxazoline compounds have insecticidal activity.
[003] The present invention provides pesticide mixtures comprising a component A and a component B, wherein component A is a compound of formula I in which L is a direct link or methylene; A1 and A2 are CH, or one of A1 and A2 is CH and the other is N; R1 is hydrogen, cyano, C1-C8 cyanoalkyl, C1-C8 alkyl, C1-C8 haloalkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl where a carbon atom is substituted by O, S, S(O) or SO2, or C3-C8 cycloalkyl, C1-C8 cycloalkyl, C3-C8 cycloalkyl, C1-C8 alkyl where a carbon atom in the cycloalkyl group is substituted by O, S, S(O) or SO2, or C3-C8 cycloalkyl, C1-C8 haloalkyl, C1-C8 hydroxyalkyl, C1-C8 alkoxy, C1-C8 alkenyl, C2-C8 haloalkenyl, C2-C8 alkynyl, C2-C8 haloalkenyl, phenyl, phenyl substituted by one to three R6, C1-C4 phenylalkyl, C1-C4 phenyl alkyl in which the phenyl moiety is substituted by one to three R6 groups, 5-6 member C1-C4 heteroaryl or 5-6 member C1-C4 heteroaryl in which the heteroaryl moiety is substituted by one to three R6 groups, or C1-C4 alkyl-(Ci-C4-ON=)C-CH2- alkyl; R2 is chlorodifluoromethyl or trifluoromethyl; Petition 870200016293, dated 03 / 02 / 2020, page 11 / 92 2 / 77 each R3 is independently bromine, chlorine, fluorine or trifluoromethyl; R4 is hydrogen, halogen, methyl, halomethyl, or cyano; R is hydrogen; or R4 and R5 together form a bridged 1,3-butadiene group; Each R6 is independently halogen, cyano, nitro, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxy, or C1-C8 haloalkoxy. p is 2 or 3; and component B is a compound selected from a) a pyrethroid including those selected from the group consisting of permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, bifenthrin, fenpropathrin, cyfluthrin (including beta-cyfluthrin), tefluthrin, etofenprox, natural pyrethrin, tetramethrin, S-bioalethrin, fenfluthrin, prallethrin and 5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; (b) an organophosphate including those selected from the group consisting of sulprofos, acephate, methyl parathion, azinphos-methyl, demetone-s-methyl, heptenofos, thiomethone, fenamifos, monocrotofos, profenofos, triazofos, methamidofos, dimethoate, phosphamidone, malathione, chlorpyrifos, phosalone, terbufos, fensulfothione, fonofos, phorate, foxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothione, fosthiazate and diazinone; c) a carbamate including those selected from the group consisting of pirimicarb, triazamate, cloetocarb, carbofuran, furatiocarb, etiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl, thiodicarb and oxamyl; d) a benzoyl urea including those selected from the group consisting of diflubenzurone, triflumurone, hexaflumurone, flufenoxurone, lufenurone and chlorfluazurone; (e) an organic tin compound including those selected from the group consisting of cyhexatin, fenbutatin oxide and azocyclotin; f) a pyrazole including those selected from the group consisting of te- Petition 870200016293, dated 03 / 02 / 2020, page 12 / 92 3 / 77 bufenpyrad and fenpyroximate; (g) a macrolide including those selected from the group consisting of abamectin, emamectin (e.g., emamectin benzoate), ivermectin, milbemycin, spinosad, azadirachtin, and spinetoram; h) an organochlorine compound including those selected from the group consisting of endosulfan (in particular alpha-endosulfan), benzene hexachloride, DDT, chlordane and dieldrin; i) an amidine including those selected from the group consisting of chlordimeform and amitraz; j) a fumigant including those selected from the group consisting of chloropicrin, dichloropropane, methyl bromide and metam; k) a neonicotinoid compound including those selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, nitiazine and flonicamid; l) a diacylhydrazine including those selected from the group consisting of tebufenozide, cromofenozide and methoxyfenozide; m) a diphenyl ether including those selected from the group consisting of diphenolane and pyriproxyfen; n) indoxacarb; o) chlorfenapyr; p) pimetrozine; q) spirotetramat, spirodiclofen and spiromesifen; r) a diamide including those selected from the group consisting of flubendiamide, chlorantraniliprole (Rynaxypyr®) and cyantraniliprole; s) sulfoxaflor; t) metaflumizone; u) fipronil and etiprol; v) pirifluquinazone; w) buprofezin; x) diafenthiurone; Petition 870200016293, dated 03 / 02 / 2020, page 13 / 92 4 / 77 y) 4-[(6-Chloro-pyridin-3-ylmethyl)-(2,2-difluoro-ethyl)-amino]-5H-furan-2-one; z) Bacillus species, and Pasteuria species; aa) flupiradifurone; ab) CAS: 915972-17-7 (WO 2006129714; WO2011 / 147953; WO2011 / 147952); ac) CAS: 26914-55-8 (WO 2007020986); (ad) a compound selected from novalurone, noviflumurone, tolfenpyrad, piriprol, milbemectin, lepimectin, metaflumizone, Essential oils such as Bugoil® - (PlantImpact), acequinocil, bifenazate, cyenopyrafene, cyflumethophene, ethoxazole, flomethoquine, fluacripyrim, fluensulfone, flufenerim, flupyradifurone, harpine, iodomethane, dodecadienol, pyridaben, pyridalil, pirimidifene, flupyradifurone.
[004] Additionally, component B may be a nematicidal active biological agent. A nematicidal active biological agent refers to any biological agent that has nematicidal activity. The biological agent may be any type known in the art, including bacteria and fungi. The term active in nematicidal terms refers to having an effect on, such as a reduction in damage caused by nematodes related to agriculture. The nematicidal active biological agent may be a bacterium or a fungus. Preferably, the biological agent is a bacterium. Examples of nematicidal active bacteria include Bacillus species, for example, Bacillus firmus, Bacillus cereus, Bacillus subtilis, and Pasteuria species such as Pasteuria penetrans and Pasteuria nishizawae. A suitable strain of Bacillus firmus is the CNCM I-1582 strain, which is commercially available as BioNem™. A suitable strain of Bacillus cereus is the CNCM I-1562 strain.More details about both strains of Bacillus can be found in US 6,406,690. Other biological organisms that may be included in the compositions of the invention are bacteria such as Streptomyces spp. as well as S. avermitilis, and fungi such as Pochonia spp. as well as P. chlamydosporia. Also of interest are Metarhizium spp. as well as M. Petition 870200016293, dated 03 / 02 / 2020, p. 14 / 92 5 / 77 anisopliae; Pochonia spp. as well as P. chlamydosporia.
[005] It has now been surprisingly discovered that the mixture of active ingredients according to the invention not only distributes about the additive intensification of the spectrum of action with respect to the pest to be controlled that was expected in principle but achieves a synergistic effect that can prolong the range of action of component A and component B in two ways. First, the application rates of component A and component B are reduced while the action remains equally good. Second, the mixture of active ingredients still achieves a high degree of pest control, sometimes even where the two individual components have become totally ineffective at such a low range of application rates. This allows for increased safety in use.
[006] However, in addition to the actual synergistic action with regard to pest control, the pesticide compositions according to the invention may have surprisingly beneficial additional properties that may also be described, in a broader sense, as synergistic activity. Examples of such beneficial properties that may be mentioned are: a broadening of the spectrum of pest control to other pests, for example to resistant strains; a reduction in the application rate of the active ingredients; adequate pest control with the aid of the compositions according to the invention, even at an application rate at which the individual compounds are totally ineffective; beneficial behavior during formulation and / or during application, for example during grinding, sieving, emulsification, dissolution or dispensing; increased storage stability; improved light stability; more beneficial degradability;Improved toxicological and / or ecotoxicological behavior; improved useful plant characteristics including: emergence, crop yield, more developed root system, increased tillering, increased plant height, larger leaf blades, fewer dead basal leaves, more resistant shoots, greener leaf color, less fertilizer required; Petition 870200016293, dated 03 / 02 / 2020, page 15 / 92 6 / 77 fewer seeds needed, more productive shoots, earlier flowering, earlier grain ripening, less lodging, increased shoot growth, improved plant vigor, and earlier germination; or any other advantages familiar to a person skilled in the art.
[007] The compounds of formula I have remarkable insecticidal properties as described in PCT / EP2010 / 068605. Components B are known, for example, from The Pesticide Manual, Fifteenth Edition, edited by Clive Tomlin, British Crop Protection Council. The compound under y) is known from DE 102006015467. Reference to components B above includes reference to their salts and any usual derivatives, such as ester derivatives.
[008] The combinations according to the invention may also comprise more than one of the active components B, if, for example, a broadening of the pest control spectrum is desired. For example, it may be advantageous in agricultural practice to combine two or three components B with any of the compounds of formula I, or with any preferred member of the group of compounds of formula I. The mixtures of the invention may also comprise other active ingredients in addition to components A and B. In other embodiments, the mixtures of the invention may include only components A and B as active ingredients in pesticide terms, for example, no more than two active ingredients in pesticide terms.
[009] Preferred substitutes are, in any combination, as set out below. A1 and A2 are preferably CH. R1 is preferably hydrogen, C1-C8 cyanoalkyl, C1-C8 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl where a carbon atom in the cycloalkyl group is substituted by O, S, S(O) or SO2, or C3-C8 cycloalkyl-C1C8 alkyl, C3-C8 cycloalkyl-C1-C8 alkyl where a carbon atom in the cycloalkyl group is substituted by O, S, S(O) or SO2, or C1-C8 haloalkyl, C1-C8 hydroxyalkyl, C1-C8 hydroxyalkyl, C2-C8 alkenyl, C2-C8 alkynyl, phenylalkyl Petition 870200016293, dated 03 / 02 / 2020, page 16 / 92 7 / 77 C1-C4 or C1-C4 phenylalkyl wherein the phenyl moiety is replaced by one to three R6, 5-6 member C1-C4 heteroaryl or 5-6 member C1-C4 heteroaryl wherein the heteroaryl moiety is replaced by one to three R6; More preferably, R1 is hydrogen, C1-C8 cyanoalkyl, C1-C8 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl where a carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO2, or C1-C8 haloalkyl, C1-C8 hydroxyalkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C4 phenylalkyl or C1-C4 phenylalkyl wherein the phenyl moiety is replaced by one to three R6, 5-6 membered C1-C4 heteroaryl alkyl or 5-6 membered C1-C4 heteroaryl alkyl wherein the heteroaryl moiety is replaced by one to three R6;Even more preferably, R1 is hydrogen, C1-C6 cyanoalkyl, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl where a carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO2, or C1-C6 haloalkyl, C1-C6 hydroxyalkyl, C1-C6 alkoxy-C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl-CH2-alkyl or phenyl-CH2- wherein the phenyl moiety is replaced by one to three R6, furanyl or furanyl substituted by one to three R6, triazolyl or triazolyl optionally substituted by one to three R6; Even more preferably, R1 is hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 hydroxyalkyl, C1-C4 alkoxy, C1-C4 alkyl, phenyl-CH2-alkyl- or phenyl-CH2- in which the phenyl moiety is substituted by one to three R6, furanyl or furanyl substituted by one to three R6, thietanyl, oxetanyl, oxo-thietanyl, or dioxo-thietanyl;Even more preferably, R1 is hydrogen, methyl, ethyl, propyl, butyl, cyclopropyl, cyclopropyl-methyl, cyclobutyl, cyclobutyl-methyl, oxetanyl, thietanyl, trifluoroethyl, difluoroethyl, allyl, propargyl, cyanomethyl, cyanoethyl, benzyl, benzyl substituted with one to three R6, or R1 is pyridyl-methyl- or pyridyl-methyl- substituted with one to three R6; Even more preferably, R1 is methyl, ethyl, cyclopropyl, cyclobutyl, oxetanyl, thietanyl, trifluoroethyl, difluoroethyl, allyl, propargyl, cyanomethyl, cyanoethyl, benzyl, benzyl substituted with one to three R6, or pyridine-methyl- or pyridine-methyl- substituted with one to three R6, even more preferably methyl, ethyl, cyclopropyl, cyclobutyl, oxetanyl, thietanyl, trifluoroethyl, difluoroethyl, allyl, propargyl, cyanomethyl; Petition 870200016293, dated 03 / 02 / 2020, page 17 / 92 8 / 77 la, cyanoethyl, benzyl, or pyridine-methyl-. Ethyl and trifluoroethyl are particularly preferred. Heteroaryl refers preferably to pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, or thiazolyl, more preferably pyridyl, pyrazolyl, furanyl, thiophenyl, or thiazolyl, more preferably pyridyl. R2 is preferentially trifluoromethyl. Preferably, each R3 is independently chlorine or fluorine, more preferably chlorine. R4 is preferentially chlorine or methyl, more preferably methyl. R5 is preferentially hydrogen. Each R6 is preferably independently halogen, cyano, C1-C8 haloalkyl, C1-C8 alkoxy or C1-C8 haloalkoxy, most preferably fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy, cyano or methoxy. p is preferably 2. L is preferably a direct link.
[0010] In one embodiment, A1 and A2 are CH; R2 is trifluoromethyl, and R5 is hydrogen.
[0011] In one embodiment, A1 and A2 are CH; R2 is trifluoromethyl, R4 is methyl, R5 is hydrogen, each R3 is chlorine, p is 2.
[0012] Compounds of formula I include at least one chiral center and may exist as compounds of formula I* or compounds of formula I**. Petition 870200016293, dated 03 / 02 / 2020, page 18 / 92 9 / 77
[0013] The compounds of formula I** are more biologically active than the compounds of formula I*. Component A may be a mixture of compounds I* and I** in any ratio, for example, in a molar ratio of 1:99 to 99:1, for example, 10:1 to 1:10, for example, a substantially higher molar ratio of 50:50. Preferably, component A is a racemic mixture of the compounds of formula I** and I* or is enantiomerically enriched for the compound of formula I**. For example, when component A is an enantiomerically enriched mixture of formula I**, the molar ratio of compound I** compared to the total amount of both enantiomers (in component A and therefore in the mixture of the invention per se) is, for example, greater than 50%, for example, at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%.In one embodiment, component A is a compound of formula I** in substantially pure form, for example, it is provided substantially in the absence of the alternative enantiomer.
[0014] Preferred compounds of formula I are shown in the Tables below. Table A: Compounds of formula (Ia)
[0015] Table A provides 354 compounds and mixtures of formula (Ia) in which R1 has the values listed in Table X below. The symbols * and ** indicate the location of the chiral centers. Table B: Compounds of formula (Ib) Petition 870200016293, dated 03 / 02 / 2020, page 19 / 92 10 / 77
[0016] Table B provides 354 compounds and mixtures of formula (Ib) in which R1 has the values listed in Table X below. The symbols * and ** indicate the location of the chiral centers. Table C: Compounds of formula (Ic)
[0017] Table C provides 354 compounds and mixtures of formula (Ic) in which R1 has the values listed in Table X below. The symbols * and ** indicate the location of the chiral centers.
[0018] Table D provides 354 compounds and mixtures of formula (Id) in which R1 has the values listed in Table X below. The symbols * and ** indicate the location of the chiral centers. Table E: Compounds of formula (Ie) Petition 870200016293, dated 03 / 02 / 2020, page 20 / 92 11 / 77 (le)
[0019] Table E provides 354 compounds and mixtures of formula (Ie) in which R1 has the values listed in Table X below. The symbols * and ** indicate the location of the chiral centers. Table F: Compound formula (If)
[0020] Table F provides 354 compounds and mixtures of formula (If) where R1 has the values listed in Table X below. The symbols * and ** indicate the location of the chiral centers.
[0021] Table X represents Table A when X is A, Table B when X is B, Table C when X is C, Table D when X is D, Table E when X is E, Table F when X is F. Numbers of compounds Stereochemistry in * Stereochemistry in ** R1 X.1 Racemic mixture Racemic mixture ethyl- X.2 Racemic mixture Racemic mixture butyl- X.3 Racemic mixture Racemic mixture but-2-yl- X.4 Racemic mixture Racemic mixture 3-bromopropyl- X.5 Racemic mixture Racemic mixture 2,2,2-trifluoroethyl- X.6 Racemic mixture Racemic mixture 3,3,3-trifluoropropyl- X.7 Racemic mixture Racemic mixture 2-methoxyethyl- X.8 Racemic mixture Racemic mixture 1-methoxyprop-2-yl- Petition 870200016293, dated 03 / 02 / 2020, page 21 / 92 12 / 77 Numbers of compounds Stereochemistry in * Stereochemistry in ** R1 X.9 Racemic mixture Racemic mixture cyclobutyl- X.10 Racemic mixture Racemic mixture 2-methyl-cyclohex-1-yl- X.11 Racemic mixture Racemic mixture phenyl-methyl- X.12 Racemic mixture Racemic mixture 1-phenyl-ethyl-1-yl- X.13 Racemic mixture Racemic mixture 2-phenyl-ethyl-1-yl- X.14 Racemic mixture Racemic mixture (3-chlorophenyl)-methyl- X.15 Racemic mixture Racemic mixture (2-fluorophenyl)-methyl- X.16 Racemic mixture Racemic mixture (4-methoxyphenyl)-methyl- X.17 Racemic mixture Racemic mixture (2-trifluoromethylphenyl)-methyl- X.18 Racemic mixture Racemic mixture (2-trifluoromethoxyphenyl)-methyl- X.19 Racemic mixture Racemic mixture (pyrid-2-yl)-methyl- X.20 Racemic mixture Racemic mixture (pyrid-3-yl)-methyl- X.21 Racemic mixture Racemic mixture (2-chloropyrid-5-yl)-methyl- X.22 Racemic mixture Racemic mixture (1-methyl-1H-imidazol-4-yl)-methyl- X.23 Racemic mixture Racemic mixture (furan-2-yl)-methyl- X.24 Racemic mixture Racemic mixture 2-(thiophen-2'-yl)-eth-1-yl- X.25 Racemic mixture Racemic mixture 2-(indol-3'-yl)-eth-1-yl- X.26 Racemic mixture Racemic mixture (1H-benzimidazol-2-yl)methyl- X.27 Racemic mixture Racemic mixture (oxetan-2-yl)-methyl- X.28 Racemic mixture Racemic mixture (tetrahydrofuran-2-yl)methyl- X.29 Racemic mixture Racemic mixture 2-([1',3']dioxolan-2'-yl)-eth-1-yl- X.30 Racemic mixture Racemic mixture 2-(morpholin-4'-yl)-eth-1-yl- X.31 Racemic mixture racemic 2-(benzo[1',3']dioxol-5'yl)-eth-1-yl-. Petition 870200016293, dated 03 / 02 / 2020, page 22 / 92 13 / 77 Numbers of compounds Stereochemistry in * Stereochemistry in ** R1 X.32 Racemic mixture Racemic mixture (2,3-dihydrobenzo[1,4]dioxin-6-yl)-methyl- X.33 Racemic mixture Racemic mixture 2-chloro-phenyl- X.34 Racemic mixture Racemic mixture 3-fluoro-phenyl- X.35 Racemic mixture Racemic mixture 2-methyl-phenyl- X.36 Racemic mixture Racemic mixture 2-chloro-6-methyl-phenyl- X.37 Racemic mixture Racemic mixture 2-trifluoromethyl-phenyl- X.38 Racemic mixture Racemic mixture 2,4-dimethoxy-phenyl- X.39 Racemic mixture Racemic mixture 3-methyl-pyrid-2-yl- X.40 Racemic mixture Racemic mixture 1,3-dimethyl-1H-pyrazol-5-yl- X.41 Racemic mixture Racemic mixture 4-methyl-thiazol-2-yl- X.42 Racemic mixture Racemic mixture 5-methyl-thiadiazol-2-yl- X.43 Racemic mixture Racemic mixture quinolin-2-yl- X.44 Racemic mixture Racemic mixture quinolin-5-yl- X.45 Racemic mixture Racemic mixture benzothiazol-6-yl- X.46 Racemic mixture Racemic mixture 4-methyl-benzothiazol-2-yl- X.47 Racemic mixture Racemic mixture tietan-3-yl- X.48 Racemic mixture Racemic mixture 1-oxo-tietan-3-yl- X.49 Racemic mixture Racemic mixture 1,1-dioxo-tietan-3-yl- X.50 Racemic mixture Racemic mixture 3-methyl-tietan-3-yl- X.51 Racemic mixture Racemic mixture oxetan-3-yl- X.52 Racemic mixture Racemic mixture Tetrahydropyran-4-yl- X.53 Racemic mixture Racemic mixture hydrogen- X.54 Racemic mixture Racemic mixture methyl- X.55 Racemic mixture Racemic mixture propyl- X.56 Racemic mixture Racemic mixture 2,2-difluoroethyl- X.57 Racemic mixture Racemic mixture 2-fluoroethyl- X.58 S Racemic mixture ethyl- X.59 S Racemic mixture butyl-. Petition 870200016293, dated 03 / 02 / 2020, page 23 / 92 14 / 77 Numbers of compounds Stereochemistry in * Stereochemistry in ** R1 X.60 S Racemic mixture but-2-yl- X.61 S Racemic mixture 3-bromopropyl- X.62 S Racemic mixture 2,2,2-trifluoroethyl- X.63 S Racemic mixture 3,3,3-trifluoropropyl- X.64 S Racemic mixture 2-methoxyethyl- X.65 S Racemic mixture 1-methoxyprop-2-yl- X.66 S Racemic mixture cyclobutyl- X.67 S Racemic mixture 2-methylcyclohex-1-yl- X.68 S Racemic mixture phenylmethyl- X.69 S Racemic mixture 1-phenylethyl-1-yl- X.70 S Racemic mixture 2-phenylethyl-1-yl- X.71 S Racemic mixture (3-chloro-phenyl)-methyl- X.72 S Racemic mixture (2-fluoro-phenyl)-methyl- X.73 S Racemic mixture (4-methoxy-phenyl)-methyl- X.74 S Racemic mixture (2-trifluoromethyl-phenyl)-methyl- X.75 S Racemic mixture (2-trifluoromethoxy-phenyl)-methyl- X.76 S Racemic mixture (pyrid-2-yl)-methyl- X.77 S Racemic mixture (pyrid-3-yl)-methyl- X.78 S Racemic mixture (2-chloro-pyrid-5-yl)-methyl- X.79 S Racemic mixture (1-methyl-1H-imidazol-4yl)-methyl- X.80 S Racemic mixture (furan-2-yl)-methyl- X.81 S Racemic mixture 2-(thiophen-2'-yl)-eth-1-yl- (oxetan-2-yl)-methyl- X.85 S Racemic mixture (tetrahydrofuran-2-yl)-. Petition 870200016293, dated 03 / 02 / 2020, page 24 / 92 15 / 77 Numbers of compounds Stereochemistry in * Stereochemistry in ** R1 methyl- X.86 S Racemic mixture 2-([1',3']dioxolan-2'-yl)-eth-1-yl- X.87 S Racemic mixture 2-(morphol-4'-yl)-eth-1-yl- X.88 S Racemic mixture 2-(benzo[1',3']dioxol-5'yl)-eth-1-yl- X.89 S Racemic mixture (2,3-dihydrobenzo[1,4]dioxin-6-yl)-methyl- X.90 S Racemic mixture 2-chlorophenyl- X.91 S Racemic mixture 3-fluorophenyl- X.92 S Racemic mixture 2-methylphenyl- X.93 S Racemic mixture 2-chloro-6-methylphenyl- X.94 S Racemic mixture 2-trifluoromethyl-phenyl- X.95 S Racemic mixture 2,4-dimethoxy-phenyl- X.96 S Racemic mixture 3-methyl-pyrid-2-yl- X.97 S Racemic mixture 1,3-dimethyl-1H-pyrazol-5-yl- X.98 S Racemic mixture 4-methyl-thiazol-2-yl- X.99 S Racemic mixture 5-methyl-thiadiazol-2-yl- X.100 S Racemic mixture quinolin-2-yl- X.101 S Racemic mixture quinolin-5-yl- X.102 S Racemic mixture benzothiazol-6-yl- X.103 S Racemic mixture 4-methyl-benzothiazol-2-yl- X.104 S Racemic mixture tietan-3-yl- X.105 S Racemic mixture 1-oxo-thietane-3-yl- X.106 S Racemic mixture 1,1-dioxo-thietane-3-yl- X.107 S Racemic mixture 3-methyl-thietane-3-yl- X.108 S Racemic mixture oxetan-3-yl X.109 S Racemic mixture Tetrahydropyran-4-yl. Petition 870200016293, dated 03 / 02 / 2020, p. 25 / 92 16 / 77 Numbers of compounds Stereochemistry in * Stereochemistry in ** R1 X.110 S Racemic mixture hydrogen X.111 S Racemic mixture methyl X.112 S Racemic mixture propyl X.113 S Racemic mixture 2,2-difluoroethyl- X.114 S Racemic mixture 2-fluoroethyl- X.115 Racemic mixture Racemic mixture isopropyl X.116 Racemic mixture Racemic mixture cyclopropyl X.117 S Racemic mixture isopropyl X.118 S Racemic mixture cyclopropyl X.119 Racemic mixture S ethyl- X.120 Racemic mixture S butyl- X.121 Racemic mixture S but-2-yl- X.122 Racemic mixture S 3-bromopropyl- X.123 Racemic mixture S 2,2,2-trifluoroethyl- X.124 Racemic mixture S 3,3,3-trifluoropropyl- X.125 Racemic mixture S 2-methoxyethyl- X.126 Racemic mixture S 1-methoxyprop-2-yl- X.127 Racemic mixture S cyclobutyl- X.128 Racemic mixture S 2-methylcyclohex-1-yl- X.129 Racemic mixture S phenylmethyl- X.130 Racemic mixture S 1-phenylethyl-1-yl- X.131 Racemic mixture S 2-phenylethyl-1-yl- X.132 Racemic mixture S (3-chlorophenyl)-methyl- X.133 Racemic mixture S (2-fluorophenyl)-methyl- X.134 Racemic mixture S (4-methoxyphenyl)-methyl- X.135 Racemic mixture S (2-trifluoromethylphenyl)-methyl- X.136 Racemic mixture S (2-trifluoromethoxyphenyl)-methyl- X.137 Racemic mixture S (pyrid-2-yl)-methyl-. Petition 870200016293, dated 03 / 02 / 2020, page 26 / 92 17 / 77 Numbers of compounds Stereochemistry in * Stereochemistry in ** R1 X.138 Racemic mixture S (pyrid-3-yl)-methyl- X.139 Racemic mixture S (2-chloro-pyrid-5-yl)-methyl- X.140 Racemic mixture S (1-methyl-1H-imidazol-4-yl)-methyl- X.141 Racemic mixture S (furan-2-yl)-methyl- X.142 Racemic mixture S 2-(thiophen-2'-yl)-ethyl-1-yl- X.143 Racemic mixture S 2-(indol-3'-yl)-ethyl-1-yl- X.144 Racemic mixture S (1H-benzimidazol-2-yl)-methyl- X.145 Racemic mixture S (oxetan-2-yl)-methyl- X.146 Racemic mixture S (tetrahydrofuran-2-yl)methyl- X.147 Racemic mixture S 2-([1',3']dioxolan-2'-yl)-et- 1-yl- ',3']dioxol-5'yl)-eth-1-yl- X.150 Racemic mixture S (2,3-dihydro-benzo[1,4]dioxin-6-yl)-methyl- X.154 Racemic mixture S 2-chloro-6-methyl-phenyl-155 Racemic mixture S 2-trifluoromethyl-phenyl- X.156 Racemic mixture S 2,4-dimethoxy-phenyl- X.157 Racemic mixture S 3-methyl-pyrid-2-yl- X.158 Racemic mixture S 1,3-dimethyl-1H-pyrazol-5-yl- X.159 Racemic mixture S 4-methyl-thiazol-2-yl- X.160 Racemic mixture S 5-methyl-thiadiazol-2-yl-. Petition 870200016293, dated 03 / 02 / 2020, page 27 / 92 18 / 77 Number of compounds Stereochemistry in * Stereochemistry in ** R1 X.161 Racemic mixture S quinolin-2-yl- X.162 Racemic mixture S quinolin-5-yl- X.163 Racemic mixture S benzothiazol-6-yl- X.164 Racemic mixture S 4-methyl-benzothiazol-2-yl- X.165 Racemic mixture S tietan-3-yl- X.166 Racemic mixture S 1-oxo-tietan-3-yl- X.167 Racemic mixture S 1,1-dioxo-tietan-3-yl- X.168 Racemic mixture S 3-methyl-tietan-3-yl- X.169 Racemic mixture S oxetan-3-yl- X.170 Racemic mixture S tetrahydropyran-4-yl- X.171 Racemic mixture S hydrogen X.172 Racemic mixture S methyl X.173 Racemic mixture S propyl X.174 Racemic mixture S 2,2-difluoroethyl- X.175 Racemic mixture S 2-fluoroethyl- X.176 SS ethyl- X.177 SS butyl- X.178 SS but-2-yl- X.179 SS 3-bromopropyl- X.180 SS 2,2,2-trifluoroethyl- X.181 SS 3,3,3-trifluoropropyl- X.182 SS 2-methoxyethyl- X.183 SS 1-methoxyprop-2-yl- X.184 SS cyclobutyl- X.185 SS 2-methylcyclohex-1-yl- X.186 SS phenylmethyl- X.187 SS 1-phenyl-ethyl-1-yl- X.188 SS 2-phenyl-ethyl-1-yl- X.189 SS (3-chlorophenyl)-methyl- X.190 SS (2-fluorophenyl)-methyl-. Petition 870200016293, dated 03 / 02 / 2020, p. 28 / 92 19 / 77 Numbers of compounds Stereoquímica em * Estereoquímica em ** R1 X.191 SS (4-metóxi-phenil)-methyla- SS (pyrid-3-yl)-methyla- X.196 SS (2-chloro-pyrid-5-yl)-methyla- 2-(indole-3'-yl)-eth-1-yl- X.201 SS (1H-benzimidazol-2-yl)methyla- X.202 SS (oxetan-2-yl)-methyla- 1-ila- X.205 SS 2-(morpholin-4'-yl)-et-1-ila- X.209 SS 3-fluoro-phenyl- X.210 SS 2-methyl-phenyl- Petition 870200016293, 02 / 03 / 2020, pág. 29 / 92 20 / 77 Numbers of compounds Stereoquímica em * Estereoquímica em ** R1 X.212 SS 2-trifluoromethyl-phenila- 4-methyl-thiazol-2-yl- X.217 SS 5-methyl-thiadiazol-2-yl- X.218 SS quinolin-2-yl- 1-oxo-thietan-3-yla- X.224 SS 1,1-dioxo-thietan-3-yla- X.225 SS 3-metil-thietan-3-yla- X.226 SS oxetan-3-yla X.227 SS Tetra-hidropiran-4-yla X.228 SS hidrogênio X.229 SS metila X.230 SS propila X.231 SS 2,2-difluoro-etila- X.232 SS 2-fluoro-etila- X.233 Mistura racêmica S isopropila X.234 Mistura racêmica S ciclopropila X.235 SS isopropila X.236 SS ciclopropila X.237 Mistura racêmica R etila- X.238 Mistura racêmica R butila- X.239 Racêmic mixture R but-2-ila- Petition 870200016293, 02 / 03 / 2020, pág. 30 / 92 21 / 77 Numbers of compounds Stereochemistry in * Stereochemistry in ** R1 X.241 Racemic mixture R 2,2,2-trifluoroethyl- X.242 Racemic mixture R 3,3,3-trifluoropropyl- X.243 Racemic mixture R 2-methoxyethyl- X.244 Racemic mixture R 1-methoxyprop-2-yl- X.245 Racemic mixture R cyclobutyl- X.246 Racemic mixture R 2-methylcyclohex-1-yl- X.247 Racemic mixture R phenylmethyl- X.248 Racemic mixture R 1-phenylethyl-1-yl- X.249 Racemic mixture R 2-phenylethyl-1-yl- X.250 Racemic mixture R (3-chlorophenyl)methyl- X.251 Racemic mixture R (2-fluoro-phenyl)-methyl- X.252 Racemic mixture R (4-methoxy-phenyl)-methyl- X.253 Racemic mixture R (2-trifluoromethyl-phenyl)-methyl- X.254 Racemic mixture R (2-trifluoromethoxy-phenyl)-methyl- X.255 Racemic mixture R (pyrid-2-yl)-methyl- X.256 Racemic mixture R (pyrid-3-yl)-methyl- X.257 Racemic mixture R (2-chloro-pyrid-5-yl)-methyl- X.258 Racemic mixture R (1-methyl-1H-imidazol-4yl)-methyl- X.259 Racemic mixture R (furan-2-yl)-methyl- X.260 Racemic mixture R 2-(thiophen-2'-yl)-eth-1-yl- X.261 Racemic mixture R 2-(indol-3'-yl)-et-1-yl- racemic R (tetrahydrofuran-2-yl)methyl- X.265 Racemic mixture R 2-([1',3']dioxolan-2'-yl)-et-. Petition 870200016293, dated 03 / 02 / 2020, p. 31 / 92 22 / 77 Numbers of compounds Stereochemistry in * Stereochemistry in ** R1 1-yl- X.266 Racemic mixture R 2-(morpholin-4'-yl)-eth-1-yl- X.267 Racemic mixture R 2-(benzo[1',3']dioxol-5'-yl)-eth-1-yl- X.268 Racemic mixture R (2,3-dihydro-benzo[1,4]dioxin-6-yl)-methyl- X.269 Racemic mixture R 2-chloro-phenyl- X.270 Racemic mixture R 3-fluoro-phenyl- X.271 Racemic mixture R 2-methyl-phenyl- X.272 Racemic mixture R 2-chloro-6-methyl-phenyl- X.273 Racemic mixture R 2-trifluoromethyl-phenyl- X.274 Racemic mixture R 2,4-dimethoxy-phenyl- X.275 Racemic mixture R 3-methyl-pyrid-2-yl- racemic R quinolin-2-yl- X.280 Racemic mixture R quinolin-5-yl X.285 Racemic mixture R 1,1-dioxo-thietane-3-yl- X.286 Racemic mixture R 3-methyl-thietane-3-yl- X.287 Racemic mixture R oxetan-3-yl X.288 Racemic mixture R Tetrahydropyran-4-yl X.289 Racemic mixture R hydrogen X.290 Racemic mixture R methyl X.291 Racemic mixture R propyl. Petition 870200016293, dated 03 / 02 / 2020, p. 32 / 92 23 / 77 Number of compounds Stereochemistry in * Stereochemistry in ** R1 X.292 Racemic mixture R 2,2-difluoroethyl- X.293 Racemic mixture R 2-fluoroethyl- X.294 SR ethyl- X.295 SR butyl- X.296 SR but-2-yl- X.297 SR 3-bromopropyl- X.298 SR 2,2,2-trifluoroethyl- X.299 SR 3,3,3-trifluoropropyl- X.300 SR 2-methoxyethyl- X.301 SR 1-methoxyprop-2-yl- X.302 SR cyclobutyl- X.303 SR 2-methylcyclohex-1-yl- X.304 SR phenylmethyl- X.305 SR 1-phenyl-ethyl-1-yl- X.306 SR 2-phenyl-ethyl-1-yl- X.307 SR (3-chlorophenyl)-methyl- X.308 SR (2-fluorophenyl)-methyl- X.309 SR (4-methoxyphenyl)-methyl- X.310 SR (2-trifluoromethylphenyl)-methyl- X.311 SR (2-trifluoromethoxyphenyl)-methyl- X.312 SR (pyrid-2-yl)-methyl- X.313 SR (pyrid-3-yl)-methyl- X.314 SR (2-chloropyrid-5-yl)-methyl- X.315 SR (1-methyl-1H-imidazol-4yl)-methyl- X.316 SR (furan-2-yl)-methyl- X.317 SR 2-(thiophen-2'-yl)-et-1-yl- Petition 870200016293, dated 03 / 02 / 2020, p. 33 / 92 24 / 77 Compound Numbers Stereochemistry in * Stereochemistry in ** R1 X.319 SR (1H-benzimidazol-2-yl)methyl- X.320 SR (oxetan-2-yl)-methyl- X.321 SR (tetra-hydrofuran-2-yl)methyl- X.322 SR. 2-([1',3']dioxolan-2'-yl)-et- 1-yl- X.323 SR 2-(morpholin-4'-yl)-et-1-yl- X.324 SR 2-(benzo[1 ',3']dioxol-5'yl)-et-1-yl- X.325 SR (2,3-hydro- benzo[1,4]dioxin-6-yl)- methyl- X.326 SR 2-chloro-phenyl- X.327 SR 3-fluoro-phenyl- X.328 SR 2-methyl-phenyl- X.329 SR 2-chloro-6-methyl-phenyl- X.329 SR 2-chloro-6-methyl-phenyl- X.330 SR 2-triyl-fluorophenyl- X.331 SR . 2,4-dimethoxy-phenyl- X.332 SR 3-methyl-pyrid-2-yla- X.333 SR 1,3-dimethyl-1 H-pyrazole-5yla- X.334 SR 4-methyl-thiazol-2-yla- X.335 SR 5-methyl-thiazol-2-yla- X.336- SR- quinoline. X.337 SR quinolin-5-yla X.338 SR benzothiazol-6-yla- X.339 SR 4-methyl-benzothiazol-2-yla- X.340 SR thiethane-3-yla- X.341 SR 1-oxo-thietan-3-yla- Petition 870200016293, of 03 / 02 / 2020, p. 34 / 92 25 / 77 Number of compounds Stereochemistry in * Stereochemistry in ** R1 X.342 SR 1,1-dioxo-thiethane-3-yl- X.343 SR 3-methyl-thiethane-3-yl- X.344 SR oxetan-3-yl X.345 SR Tetrahydropyran-4-yl X.346 SR hydrogen X.347 SR methyl X.348 SR propyl X.349 SR 2,2-difluoroethyl- X.350 SR 2-fluoroethyl- X.351 Racemic mixture R isopropyl X.352 Racemic mixture R cyclopropyl X.353 SR isopropyl X.354 SR cyclopropyl
[0022] The present invention includes all isomers of the compounds of formula (I), their salts and N-oxides, including enantiomers, diastereomers and tautomers. Component A may be a mixture of any type of isomer of a compound of formula I, or it may be substantially a single type of isomer.
[0023] In one embodiment of the invention, component B is a compound selected from pimetrozine and flonicamid; an organophosphate selected from the group consisting of sulprofos, acephate, methyl parathion, azinphos-methyl, demetone-s-methyl, heptenofos, thiomethone, fenamifos, monocrotofos, profenofos, triazofos, methamidofos, dimethoate, phosphamidene, malathione, chlorpyrifos, phosalone, terbufos, fensulfothione, fonofos, phorate, foxim, pirimifos-methyl, pirimifos-ethyl, fenitrothione, fosthiazate and diazinon; a pyrethroid selected from the group consisting of permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, etofenprox, natural pyrethrin, tetramethrin, S-bioallethrin, fenfluthrin, prallethrin and carboxylate of Petition 870200016293, dated 03 / 02 / 2020, page 35 / 92 26 / 77 5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxo-thiolan-3-ylidenemethyl) cyclopropane; a macrolide selected from the group consisting of abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad, azadirachtin, and spinetoram; a diamide selected from the group consisting of flubendiamide, chlorantraniliprole (Rynaxypyr®) and cyantraniliprole; a neonicotinoid compound selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, nitiazine and flonicamid; spirotetramat, spirodiclofen, and spiromesifene; and sulfoxaflor, lufenerone, diafenthiurone, and fipronil.
[0024] In one embodiment, component B is a compound selected from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda-cyhalothrin, pimetrozine, spirotetramat, thiamethoxam, clothianidin, imidacloprid, chlorantraniliprole, flonicamid, sulfoxaflor, lufenerone, diafenthiuron, flubendiamide, tefluthrin, diafenthiuron and fipronil.
[0025] In one embodiment, component B is a compound selected from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda-cyhalothrin, pimetrozine, spirotetramat, thiamethoxam, clothianidin, imidacloprid, diafenthiurone, and flonicamid.
[0026] In one embodiment, component B is a compound selected from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda-cyhalothrin, diafenthiurone, pimetrozine, spirotetramat, thiamethoxam, clothianidin, imidacloprid, and chlorantraniliprole.
[0027] In one embodiment, component B is a compound selected from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda-cyhalothrin, diafenthiurone, pimetrozine, spirotetramat and thiamethoxam.
[0028] In one embodiment, component B is a compound selected from the group consisting of Petition 870200016293, dated 03 / 02 / 2020, page 36 / 92 27 / 77 a pyrethroid including those selected from the group consisting of permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, bifenthrin, fenpropathrin, cyfluthrin (including beta-cyfluthrin), tefluthrin, etofenprox, natural pyrethrin, tetramethrin, S-bioallethrin, fenfluthrin, prallethrin and 5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; a neonicotinoid compound including those selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, nitiazine and flonicamid; and diafenthiurone.
[0029] In one embodiment, component B is a compound selected from the group consisting of thiamethoxam, lambda-cyhalothrin and diafenthiurone, preferably thiamethoxam and lambda-cyhalothrin.
[0030] In one embodiment, and of particular interest for seed care, component B is a compound selected from tefluthrin, abamectin, spinosad, spinetoram, chlorpyrifos, thiodicarb, chlorantraniliprole, cyantraniliprole, Bacillus firmus, Bacillus subtilis, Pasteuria spp. (e.g., P. penetrans, P. nishizawae), imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, nitiazine, flonicamid, fipronil, pirifluquinazone, pimetrozine, sulfoxaflor and spirotetramat.
[0031] The invention also includes the following combinations: A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + abamectin. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + chlorpyrifos. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + cyantraniliprole. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + emactin. A mixture of a compound of formula I selected from Tables A, B, Petition 870200016293, dated 03 / 02 / 2020, p. 37 / 92 28 / 77 C, D, E and F + cyhalothrin. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + lambda cyhalothrin. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + gamma cyhalothrin. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + pimetrozine. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + spirotetramat. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + thiamethoxam. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + chlorantraniliprole. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + profenofos. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + acephate. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + azinphos-methyl. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + methamidophos. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + spinosad. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + spinetoram. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + flonicamid. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + indoxacarb. A mixture of a compound of formula I selected from Tables A, B, Petition 870200016293, dated 03 / 02 / 2020, p. 38 / 92 29 / 77 C, D, E and F + spirodiclofen. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + spiromesifen. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + sulfoxaflor. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + fipronil. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + imidacloprid. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + thiacloprid. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + acetamiprid. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + nitenpyram. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + dinotefuran. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + clothianidin. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + nitiazine. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + pyriproxyfen. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + buprofezin. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + pirifluquinazone. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + thiamethoxam and cyantraniliprole. A mixture of a compound of formula I selected from Tables A, B, Petition 870200016293, dated 03 / 02 / 2020, p. 39 / 92 30 / 77 C, D, E and F + thiamethoxam and chlorantraniliprole. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + sulfoxalor. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + lufenerone. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + diafenthiurone. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + flubendiamide. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + tefluthrin. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + fipronil. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + thiodicarb. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + Bacillus firmus. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + Bacillus subtilis. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + P. penetrans. A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + P. nishizawae.
[0032] In one embodiment, the ratio of compound of formula I to abamectin by weight in the composition may be 1:0.05 to 1:1. Examples of ratios falling within this range include 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9. When used for soil application, the ratio of compound of formula I to abamectin may be up to 1:1.3.
[0033] In one embodiment, the ratio of the compound of formula I to chlorpyrifos by weight in the composition can be 1:1 to 1:10. Examples of ratios Petition 870200016293, dated 03 / 02 / 2020, p. 40 / 92 31 / 77 falling within this range include 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9.
[0034] In one embodiment, the ratio of the compound of formula I to cyantraniliprole by weight in the composition may be 1:0.2 to 1:4. Examples of ratios falling within this range include 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5.
[0035] In one embodiment, the ratio of the compound of formula I to emamectin by weight in the composition may be 1:0.05 to 1:1. Examples of ratios falling within this range include 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9.
[0036] In one embodiment, the ratio of the compound of formula I to lambda cyhalothrin by weight in the composition can be 1:0.1 to 1:2. Examples of ratios falling within this range include 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8. In another embodiment, the ratio of the compound of formula I to lambda cyhalothrin by weight in the composition is at least 1:1000, at least 1:500, at least 1:100. For example, this ratio of the compound of formula I to lambda cyhalothrin is, for example, 1:250 to 250:1, for example, 1:250 to 10:1, for example, 1:250 to 1:1.
[0037] In one embodiment, the ratio of the compound of formula I to pimetrozine by weight in the composition may be 1:1 to 1:6. Examples of ratios falling within this range include 1:2, 1:3, 1:4, 1:5. When used for soil application, the ratio of the compound of formula I to pimetrozine may be up to 1:10; additional examples include 1:7, 1:8, 1:9.
[0038] In one embodiment, the ratio of the compound of formula I to spirotetramat by weight in the composition may be 1:0.5 to 1:4. Examples of ratios falling within this range include 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5.
[0039] In one embodiment, the ratio of the compound of formula I to thiamethoxam by weight in the composition may be 1:0.5 to 1:6. Examples of ratios falling within this range include 1:1, 1:2, 1:3, 1:4, and 1:5. In another embodiment, the ratio of the compound of formula I to thiamethoxam by weight in the composition may be at least 1:4000, at least 1:1000, at least Petition 870200016293, dated 03 / 02 / 2020, p. 41 / 92 32 / 77 1:100. For example, the ratio of the compound of formula I to thiamethoxam is, for example, 1:250 to 250:1, for example, 1:250 to 10:1, and for example, 1:250 to 1:1.
[0040] In one embodiment, the ratio of the compound of formula I to clothianidin by weight in the composition can be 1:0.5 to 1:6. Examples of ratios falling within this range include 1:1, 1:2, 1:3, 1:4, and 1:5.
[0041] In one embodiment, the ratio of the compound of formula I to imidacloprid by weight in the composition can be 1:0.5 to 1:6. Examples of ratios falling within this range include 1:1, 1:2, 1:3, 1:4, and 1:5.
[0042] In one embodiment, the ratio of the compound of formula I to chlorantraniliprole by weight in the composition can be 1:0.2 to 1:4. Examples of ratios falling within this range include 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5.
[0043] In one embodiment, the ratio of the compound of formula I to sulfoxaphor by weight in the composition can be 1:0.5 to 1:6. Examples of ratios falling within this range include 1:1, 1:2, 1:3, 1:4, and 1:5.
[0044] In one embodiment, the ratio of the compound of formula I to diafenthiurone by weight in the composition may be 1:1.5 to 1:80, for example, 1:0.5 to 1:6. Examples of ratios falling within this range include 1:1, 1:2, 1:3, 1:4, and 1:5. In another embodiment, the ratio of the compound of formula I to diafenthiurone by weight in the composition may be at least 1:500, at least 1:250, at least 1:100. For example, this ratio of the compound of formula I to diafenthiurone may be, for example, 1:250 to 250:1, for example, 1:250 to 10:1, for example, 1:250 to 1:1.
[0045] The compounds of the invention can be prepared by a variety of methods as shown in Schemes 1 to 3. Scheme 1 Petition 870200016293, dated 03 / 02 / 2020, p. 42 / 92 33 / 77 1) Compounds of formula (I) can be prepared by reacting a compound of formula (II) wherein R is OH, alkoxy Ci-Ce or Cl, F or Br, with an amine of formula (III) as shown in Scheme 1. When R is OH, such reactions are usually carried out in the presence of a coupling reagent, such as N,N'-dicyclohexylcarbodiimide (DCC), 1-ethyl-3(3-dimethylaminopropyl)carbodiimide hydrochloride (EDO) or bis(2-oxo-3oxazolidinyl)phosphonic chloride (BOPI-Cl), in the presence of a base, and optionally in the presence of a nucleophilic catalyst, such as hydroxybenzotriazole (HOBT). When R is Cl, such reactions are usually carried out in the presence of a base, and optionally in the presence of a nucleophilic catalyst. Alternatively, it is possible to conduct the reaction in a two-phase system comprising an organic solvent, preferably ethyl acetate, and an aqueous solvent, preferably a sodium bicarbonate solution.When R is a C1-C1 alkoxy, it is sometimes possible to convert the ester directly to the amide by heating the ester and amine together in a thermal process. Suitable bases include pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP), or diisopropylethylamine (Hunig base). Preferred solvents are A / ,A / -dimethylacetamide, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, ethyl acetate, and toluene. The reaction is carried out at a temperature of 0°C to 100°C, preferably 15°C to 30°C, particularly at room temperature. Amines of formula (III) are known from the literature or can be prepared using methods known to a person skilled in the art. 2) Acid halides of formula (II), where R is Cl, F, or Br, can be pre Petition 870200016293, dated 03 / 02 / 2020, p. 43 / 92 34 / 77 stopped from carboxylic acids of formula (II), where R is OH, under standard conditions, as described for example in WO2009 / 080250. 3) Carboxylic acids of formula (II), where R is OH, can be formed from esters of formula (II), where R is alkoxy Ci-Ce as described for example in WO2009 / 080250. 4) Compounds of formula (I) can be prepared by reacting a compound of formula (IV) wherein XB is a leaving group, for example a halogen such as bromine, with carbon monoxide and an amine of formula (III), in the presence of a catalyst such as palladium(II) acetate or bis(triphenylphosphine)palladium(II) dichloride, optionally in the presence of a ligand such as triphenylphosphine and a base such as sodium carbonate, pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP) or diisopropylethylamine (Hunig's base), in a solvent such as water, / V, / V-dimethylformamide or tetrahydrofuran. The reaction is carried out at a temperature of 50 °C to 200 °C, preferably 100 °C to 150 °C. The reaction is carried out at a pressure of 5 to 20 MPa (50 to 200 bar), preferably 10 to 15 MPa (100 to 150 bar). 5) Compounds of formula (IV) wherein XB is a leaving group, for example a halogen such as bromine, can be prepared by a variety of methods, for example as described in WO2009 / 080250. Scheme 2 Petition 870200016293, dated 03 / 02 / 2020, p. 44 / 92 35 / 77 6) Alternatively, compounds of formula (I) can be prepared by various methods from an intermediate of formula (V) as shown in Scheme 2 where XB is a leaving group, for example a halogen such as bromine, or XB is cyano, formyl or acetyl according to methods similar to those described in WO09080250. An intermediate of formula (V) can be prepared for example from an intermediate of formula (VI) as described in the same reference. Scheme 3 7) Alternatively, compounds of formula (I) can be prepared by various methods from an intermediate of formula (VII) as shown in Scheme 3 where Xc-1 or Xc-2 in accordance with methods similar to those described in WO2009 / 080250. 8) Compounds of formula (VII) in which Xc-1 or Xc-2 are prepared from a compound of formula (Va) from a compound of formula (VII) in which Xc-1 or Xc-2 are prepared using methods similar to those Petition 870200016293, dated 03 / 02 / 2020, p. 45 / 92 36 / 77 described in WO2009 / 080250. 9) Compounds of formula (VII) in which XCé CH2-halogen, such as bromine or chlorine, can be prepared by reacting a methyl ketone of formula (Va) with a halogenating agent, such as bromide or chloride, in a solvent, such as acetic acid, at a temperature of 0 °C to 50 °C, preferably from room temperature to 40 °C. [00 46] Other methods for the preparation of compounds of formula I are described in PCT / EP2010 / 068605, which is incorporated herein by reference.
[0047] The present invention also relates to a method of controlling insects, mites, nematodes or mollusks which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a combination of components A and B; seeds comprising a mixture of components A and B; and a method comprising coating a seed with a mixture of components A and B.
[0048] Components A and B can be proportioned and / or used in quantities that allow for synergistic pest control. For example, the present invention includes pesticide mixtures comprising a component A and a component B in a synergistically effective quantity; agricultural compositions comprising a mixture of components A and B in a synergistically effective quantity; the use of a mixture of components A and B in a synergistically effective quantity for animal pest control; a method of animal pest control which comprises contacting the animal pests, their habitat, breeding site, food source, 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 locations to be protected from animal attack or infestation with a mixture of components A and B in a synergistically effective quantity;a method for protecting crops from attack or infestation by animal pests, which comprises contacting a crop with a mixture of components A and B in a synergistically effective quantity; a method for protecting seeds; Petition 870200016293, dated 03 / 02 / 2020, p. 46 / 92 37 / 77 of soil and root and seedling shoot insects, soil and foliar insects comprising contacting the seeds before sowing and / or after pre-germination with a mixture of components A and B in a synergistically effective amount; seeds comprising, for example, coated with a mixture of components A and B in a synergistically effective amount; a method comprising coating a seed with a mixture of components A and B in a synergistically effective amount; a method of controlling insects, mites, nematodes and molluscs which comprises applying to a pest, a pest locus, or a plant susceptible to attack by a pest a combination of components A and B in a synergistically effective amount. The mixtures of A and B will normally be applied in an amount effective in terms of insecticides, acaricides, nematicides or molluscicides. In the application, components A and B may be applied simultaneously or separately.
[0049] According to the invention, useful plants typically comprise the following plant species: grapevines; cereals, such as wheat, barley, rye or oats; beetroot, such as sugar beet or fodder beet; fruits, such as pome fruits, 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; oilseed plants, such as rapeseed, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or peanuts; cucumber plants, such as zucchini, cucumbers or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruits or tangerines; Vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, cucurbits or paprika; laurel plants, such as avocados, cinnamon or camphor; corn; tobacco; nuts; coffee;Sugar cane; tea; grapevines; hops; durian; bananas; natural rubber plants; grass or ornamental plants, such as flowers, shrubs, broad-leaved or evergreen trees, for example, conifers. This list does not represent; Petition 870200016293, dated 03 / 02 / 2020, page 47 / 92 38 / 77 does not present any limitations. It may be noted that the compound of formula I can also be used for the control of insect, mite, mollusc and / or nematode pests in grass in the absence of mixing partners.
[0050] The term useful plants is to be understood as also including useful plants that have been made tolerant to herbicides such as bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example, primisulfurone, prosulfurone and trifloxysulfurone, EPSPS (5-enol-pyrovil-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional breeding methods or genetic engineering. An example of a crop that has been made tolerant to imidazolinones, for example, imazamox, by conventional breeding methods (mutagenesis) is Clearfield® summer rapeseed (Canola). Examples of crops that have been made tolerant to herbicides or herbicide classes through genetic engineering methods include commercially available glyphosate- and glufosinate-resistant corn varieties under the trademarks RoundupReady®, Herculex I®, and LibertyLink®.
[0051] The term useful plants is to be understood as also including useful plants that have been transformed by the use of recombinant DNA techniques so that they are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
[0052] The compounds of formula I and mixtures of the invention can be used in transgenic plants (including cultivars) obtained by genetic engineering methods and / or by conventional methods. These are understood to mean plants having new properties (traits) that have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. Depending on the plant species or plant cultivars, their location and growing conditions (soils, climate, growing season, diet), treatment according to the invention may also result in synergistic superadditive effects. Petition 870200016293, dated 03 / 02 / 2020, p. 48 / 92 39 / 77
[0053] Thus, for example, reduced application rates and / or a broadening of the spectrum of activity and / or an increase in the activity of substances and compositions that can be used according to the invention are possible, improved plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or water or salt content in the soil, increased flowering performance, easier harvesting, accelerated maturation, higher crop yields, higher quality and / or higher nutritional value of harvested products, improved storage stability and / or processability of harvested products, which exceed the effects that were actually expected. Such synergistic effects with the transgenic crop can be obtained when applied for soil pest control (e.g., seed care or furrow treatments) as well as after emergence, particularly for maize and soybeans.
[0054] The use of compounds of formula I and mixtures of the invention can also be applied as a seed care treatment with transgenic crops in resistance management strategies for the trait (particularly insecticidal traits), for example, including in corn and soybeans.
[0055] The preferred transgenic plants or plant cultivars to be treated according to the invention include all plants which, by virtue of genetic modification, have received genetic material that confers particularly advantageous and useful characteristics on these plants. Examples of such traits are improved plant growth, increased tolerance to drought or water or salt content in the soil, enhanced flowering performance, easier harvesting, accelerated ripening, higher crop yields, higher quality and / or higher nutritional value of the harvested products, improved storage stability and / or processability of the harvested products.
[0056] Additional and particularly emphasized examples of such traits are improved plant defense against animal and microbial pests, such as insects, mites, fungi, bacteria and / or phytopathogenic viruses, and Petition 870200016293, dated 03 / 02 / 2020, page 49 / 92 40 / 77 also increases plant tolerance to certain active compounds in herbicide terms.
[0057] Examples of transgenic plants that can be mentioned are important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, sugar beets, tomatoes, peas and other vegetable varieties, cotton, tobacco, rapeseed and also fruit plants (with fruits such as apples, pears, citrus fruits and grapes).
[0058] The compounds of formula I and mixtures of the invention can be used in transgenic plants that are capable of producing one or more pesticidal proteins that confer on the transgenic plant tolerance or resistance to harmful pests, for example, insect pests, nematode pests and the like. Such pesticidal proteins include, without limitation, Cry proteins from Bacillus thuringiensis Cry1Ab, Cry1Ac, Cry1F, Cry2Ab, Cry2Ae, Cry3A, Cry3Bb or Cry9C; manipulated proteins such as modified Cry3A (US Patent 7,030,295) or Cry1A.105; or vegetative insecticidal proteins such as Vip1, Vip2 or Vip3. A complete list of Bt Cry proteins and VIPs useful in the invention can be found on the global network in the Bacillus thuringiensis Toxin Nomenclature database maintained by the University of Sussex (see also, Crickmore et al. (1998) Microbiol. Mol. Biol. Rev. 62: 807-813).Other useful pesticidal proteins in the invention include proteins from bacteria that colonize nematodes, for example, Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins; plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, or papain inhibitors; ribosome-inactivating proteins (RIPs), such as ricin, corn RIP, abrin, lufin, saporin, or briodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyltransferase, cholesterol oxidases, inhibitors of... Petition 870200016293, dated 03 / 02 / 2020, pp. 50 / 92 41 / 77 ecdysone or HMG-CoA reductase; ion channel blockers, such as sodium or calcium channel blockers; juvenile hormone esterase; diuretic hormone receptors (helicoquinine receptors); stilbene synthase, bibenzyl synthase, chitinases or guanases. Additional examples of such pesticidal proteins or transgenic plants capable of synthesizing such proteins are disclosed, for example, in EP-A 374753, WO 93 / 007278, WO 95 / 34656, EP-A 427529, EP-A 451878, WO 03 / 18810 and WO 03 / 52073.The methods for producing such transgenic plants are generally known to those skilled in the art, and some of them are commercially available, such as Agrisure®CB (P1) (corn producing Cry1Ab), Agrisure®RW (P2) (corn producing mCry3A), Agrisure® Viptera (P3) (corn hybrids producing Vip3Aa); Agrisure300GT (P4) (corn hybrids producing Cry1Ab and mCry3A); YieldGard® (P5) (corn hybrids producing the Cry1Ab protein), YieldGard® Plus (P6) (corn hybrids producing Cry1Ab and Cry3Bb1), Genuity® SmartStax® (P7) (corn hybrids with Cry1A).105, Cry2Ab2, Cry1F, Cry34 / 35, Cry3Bb); Herculex® I (P8) (corn hybrids producing Cry1Fa) and Herculex®RW (P9) (corn hybrids producing Cry34Ab1, Cry35Ab1 and the enzyme Phosphinotricin-N-Acetyltransferase [PAT]); NuCOTN®33B (P10) (cotton cultivars producing Cry1Ac), Bollgard®I (P11) (cotton cultivars producing Cry1Ac), Bollgard®II (P12) (cotton cultivars producing Cry1Ac and Cry2Ab2) and VIPCOT® (P13) (cotton cultivars producing a Vip3Aa). Soybeans resistant to Soybean Cyst Nematode (SCN® - Syngenta (P14)) and soybeans with aphid-resistant trait (AMT® (P15)) are also of interest.
[0059] Additional examples of such transgenic crops are: 1. Bt11 maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10 (P16). Genetically modified Zea mays that has been made resistant to attack by the European maize borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CryIA(b) toxin. Bt11 maize also transgenically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium. Petition 870200016293, dated 03 / 02 / 2020, pp. 51 / 92 42 / 77 nio. 2. Bt176 maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10 (P17). Genetically modified Zea mays that has been made resistant to attack by the European maize borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CryIA(b) toxin. Bt176 maize also transgenically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10 (P18). Maize that has been made insect-resistant by transgenic expression of a modified CryIIIA toxin. This toxin is Cry3A055 modified by the 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 SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9 (P19). MON 863 expresses a CryIIIB(b1) toxin and has resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02. (P20) 6. Maize 1507 from Pioneer Overseas Corporation, Avenue Tedesco, 7 B1160 Brussels, Belgium, registration number C / NL / 00 / 10. (P21) Maize genetically modified to express the Cry1F protein to achieve resistance to certain Lepidoptera insects and the PAT protein to achieve tolerance to the herbicide glufosinate ammonium. 7. NK603 x MON 810 maize from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03 (P22). It consists of conventionally improved hybrid maize varieties obtained by crossing the genetically modified varieties NK603 and MON 810. The NK603 χ MON 810 maize transgenically expresses the CP4 EPSPS protein, obtained from the Agrobacterium sp. strain CP4, which provides tolerance. Petition 870200016293, dated 03 / 02 / 2020, pp. 52 / 92 43 / 77 contains the herbicide Roundup® (contains glyphosate), and also a CryIA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki that provides tolerance to certain Lepidoptera, including the European corn borer.
[0060] Additional examples of transgenic plants, and of very high interest, are those exhibiting traits conferring resistance to 2,4-D (e.g., Enlist®) (e.g., WO 2011066384) (P23), glyphosate (e.g., Roundup Ready®, Roundup Ready 2 Yield® (P25)), sulfonylurea (e.g., STS®), glufosinate (e.g., Liberty Link®, Ignite®), Dicamba tolerance (Monsanto), HPPD (e.g., isoxaflutol herbicide, mesotrione herbicide - US7312379) (Bayer CropScience, Syngenta). Double or triple stacks of any of the traits described here are also of interest, including tolerance to glyphosate and sulfonylurea (e.g., Optimum GAT®), plants stacked with STS® and Roundup Ready®, or plants Stacked with STS® and Roundup Ready 2 Yield®, dicamba and glyphosate tolerance (Monsanto). Of particular interest are soybean plants exhibiting traits conferring resistance to 2.4D (e.g., Enlist®), glyphosate (e.g., Roundup Ready®, Roundup Ready 2 Yield®), sulfonylurea (e.g., STS®), glufosinate (e.g., Liberty Link®, Ignite®), dicamba tolerance (Monsanto), and HPPD (e.g., isoxaflutol herbicide) (Bayer CropScience, Syngenta). Double or triple stacking in soybean plants of any of the traits described here are also of interest, including glyphosate and sulfonylurea tolerance (e.g., Optimum GAT®, plants stacked with STS® and Roundup Ready® or Roundup Ready 2 Yield®), dicamba and glyphosate tolerance (Monsanto).
[0061] Transgenic crops of insect-resistant plants are also described in BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http: / / bats.ch).
[0062] The term locus of a useful plant as used herein is intended to encompass the location where useful plants are growing, where propagation materials for useful plants are sown, or where propagation materials are grown. Petition 870200016293, dated 03 / 02 / 2020, pp. 53 / 92 44 / 77 Useful plants will be placed in the soil. An example of such a locus is a field in which cultivated plants are growing.
[0063] 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. Examples may include seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and plant parts. Germinated plants and young plants that are to be transplanted after germination or after emergence from the soil may also be mentioned. These young plants may be protected before transplanting by total or partial immersion treatment. Preferably, plant propagation material is understood to denote seeds. Insecticides that are of particular interest for seed treatment include thiamethoxam, imidacloprid, and clothianidin. Accordingly, in one embodiment, component B is selected from thiamethoxam, imidacloprid, and clothianidin.
[0064] Methods for applying or treating active ingredients to plant propagation material, especially seeds, are known in the art, and include methods of applying treatment, coating, pelleting, and soaking the propagation material. Conventional treatment techniques and machines may be used, such as fluidized beds, roller mills, rotostatic seed treaters, drum coaters, and spouted beds.
[0065] Application methods in the soil may be through any suitable method which ensures that the combination penetrates the soil, for example, nursery tray application, furrow application, soil soaking, soil injection, drip irrigation, application through sprayers or center pivot, soil incorporation (wide diffusion or band application) are such methods. Alternatively or additionally, one or more materials may be applied to a suitable substrate, for example a seed that Petition 870200016293, dated 03 / 02 / 2020, pp. 54 / 92 45 / 77 is not intended for germination, and sow the substrate treated with plant propagation material.
[0066] Uniform distribution of ingredients and good adhesion are particularly desirable for seed treatment. The treatment can vary from a thin film or formulation treatment, for example, a mixture of active ingredients, on a plant propagation material, such as a seed, where the original size and / or shape are recognizable, to an intermediate state, a thicker film such as pelleting with many layers of different materials (such as carriers, for example, clays; different formulations, such as of other active ingredients; polymers; and colorants) where the original shape and / or size of the seed are no longer recognizable.
[0067] Application in seed propagation material may include controlled-release coatings, wherein the ingredients of the combinations are incorporated into materials that release the ingredients over time. Examples of controlled-release technologies are generally known in the art and include polymer films and waxes, wherein the ingredients may be incorporated into the controlled-release material or applied between layers of materials, or both.
[0068] A further aspect of the present 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 pest attack, comprising applying to said natural substances of plant and / or animal origin or their processed forms a combination of components A and B in a synergistically effective amount. Such applications include using the mixtures of the invention as a treatment, for example a fumigant, for stored grain to protect against attack by invertebrate pests and / or fungi. It may be noted that compounds of formula I can be used alone as a treatment for stored grain to protect against attack by invertebrate pests.
[0069] According to the present invention, the term natural substances Petition 870200016293, dated 03 / 02 / 2020, pp. 55 / 92 46 / 77 of plant origin, which have been taken from the natural life cycle, denotes plants or parts thereof that have been harvested from the natural life cycle and are in freshly harvested form. Examples of such natural substances of plant origin are stems, leaves, tubers, seeds, fruits, or grains. According to the present 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 into a more storable form of the substance (a storage good). Examples of such modification processes are pre-drying, moistening, crushing, fragmentation, grinding, compression, or toasting.Also falling under the definition of a processed form of a natural substance of plant origin is wood, whether in the form of raw timber, such as timber for construction, electricity poles and barriers, or in the form of finished articles, such as furniture or objects made of wood.
[0070] According to the present 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, skins, fur and the like.
[0071] 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 pest attack, which comprises applying to said natural substances of plant and / or animal origin or their processed forms a combination of components A and B in a synergistically effective quantity.
[0072] An additional preferred embodiment is a method of protecting fruits, preferably pome fruits, stone fruits, soft fruits and citrus fruits, that have been removed from their natural life cycle, and / or their processed forms, which comprises applying to said fruits and / or their processed forms a combination of components A and B in a synergistically determined amount. Petition 870200016293, dated 03 / 02 / 2020, pp. 56 / 92 47 / 77 is effective.
[0073] The compounds of formula (I) and mixtures of the invention can be used to combat and 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, mite, nematode and mollusc pests. Insects, mites, nematodes and molluscs are hereinafter collectively referred to as pests. The pests that can be combated and controlled by the use of the compounds of the invention include those pests associated with agriculture (the term includes the cultivation of crops for food and fiber products), horticulture, animal husbandry, pets, forestry and the storage of plant-based products (such as fruits, grains and wood); those pests associated with damage to man-made structures and the transmission of human and animal diseases; and also annoying pests (such as flies).The compounds of the invention can be used, for example, on grass, ornamental plants such as flowers, shrubs, broadleaf or evergreen trees, for example conifers, as well as for injection into trees, pest management and the like. Compositions comprising the compound of formula I can be used on ornamental garden plants (e.g., flowers, shrubs, broadleaf or evergreen trees), for example, to control aphids, whiteflies, scale insects, mealybugs, beetles and caterpillars. Compositions comprising the compound of formula I can be used on garden plants (e.g., flowers, shrubs, broadleaf or evergreen trees), on indoor plants (e.g., flowers and shrubs) and on indoor pests, for example, to control aphids, whiteflies, scale insects, mealybugs, beetles and caterpillars.
[0074] Furthermore, the compounds of formula (I) and mixtures of the invention can be effective against harmful insects without substantially imposing any harmful side effects on cultivated plants. The application of the compounds of the invention can increase crop yields and can Petition 870200016293, dated 03 / 02 / 2020, pp. 57 / 92 48 / 77 improve the quality of the harvested material. The compounds of the invention may have favorable properties with regard to the amount applied, residue formulation, selectivity, toxicity, production methodology, high activity, broad spectrum of control, safety, control of resistant organisms, for example, pests that are resistant to phosphorus agents and / or organic carbamate agents.
[0075] Examples of pest species that can be controlled by the compounds of formula (I) and mixtures of the invention include: coleoptera, for example, Callosobruchus chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Monochamus alternatus, Lissorhoptrus oryzophilus, Lyctus bruneus, Aulacophora femoralis; lepidoptera, for example, Lymantria dispar, Malacosoma neustria), Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis), Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotisfucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens, Phyllocnistis citrella; hemiptera, for example, Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicas, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nezara spp., Trialeurodes vaporariorm, Psylla spp.; tisanoptera, e.g. Thrips palmi, Franklinella occidental; orthoptera, e.g. Blatella germanica, Periplaneta americana, Gryllotalpa Africana, Locusta migratoria migratoriodes; isoptera, e.g. Reticulitermes speratus, Coptotermes formosanus; diptera, for example, Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles sinensis, Culex tritaeniorhynchus, Liriomyza trifolii; mites, e.g. Tetranychus cinnabarinus, Tetranychus urticae, Panonychus citri, Aculops pelekassi, Tarsonemus spp.; nematodes, for example, Meloidogyne incognita, Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides besseyi, Heterodera glycines, Pratylenchus spp.
[0076] Examples of additional pest species that can be controlled Petition 870200016293, dated 03 / 02 / 2020, pp. 58 / 92 49 / 77 ladas pelos composados da formula (I) e mistura da invenção include: da ordem dos Anoplura (Phthiraptera), por exemplo, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.; from the class of Arachnida, for example, Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici; from the class of Bivalva, for example, Dreissena spp.; give the order of the Chilopoda, for example, Geophilus spp., Scutigera spp.; of the order of Coleoptera, for example, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.; of the order of Collembola, for example. Petition 870200016293, dated 03 / 02 / 2020, pp. 59 / 92 50 / 77 Onychiurus armatus; of the order of Dermaptera, for example, Forficula auricularia; of the order of Diplopoda, for example, Blaniulus guttulatus; of the order of Diptera, for example, Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia spp., Tipula paludosa, Wohlfahrtia spp.; give the class Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.; give a class of two helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti; pode ser alem do mais possibile controlar protozoários, tais como Eimeria; give the order of Heteroptera, for example, Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae,. Petition 870200016293, dated 02 / 03 / 2020, p. 60 / 92 51 / 77 Piesma quadrata, Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.; da ordem dos Homoptera, for example, Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii; from the order of Hymenoptera, for example, Diprion spp., Hoplocampa spp., La. Petition 870200016293, dated 02 / 03 / 2020, p. 61 / 92 52 / 77 sius spp., Mono-morium pharaonis, Vespa spp.; of the order of Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber; of the order of Isoptera, for example, Reticulitermes spp., Odontotermes spp.; of the order of Lepidoptera, for example, Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp., Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella, Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema oryzae, Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp.; from the order of Orthoptera, for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria; from the order of Siphonaptera, for example, Ceratophyllus spp., Xenopsylla cheopis. From the order of Symphyla, for example, Scutigerella immaculata; from the order of Thysanoptera, for example, Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.; from the order of Thysanura, for example, Lepisma saccharina.Phytoparasitic nematodes include, for example, Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp.,. Petition 870200016293, dated 03 / 02 / 2020, pages 62 / 92 53 / 77 Tylenchulus semipenetrans, Xiphinema spp.
[0077] The combinations according to the present invention are moreover particularly effective against the following pests: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (fulgoromorphs), Nephotettix incticeps (leafhopper), Nezara spp. (true bugs), Euschistus spp. (true bugs), Leptocorisa spp. (true bugs), Frankliniella occidentalis (thrips), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (cotton boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp.(whiteflies), Bemisia tabaci (whitefly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton looper), Heliothis virescens (tobacco caterpillar), Helicoverpa armigera (corn earworm), Helicoverpa zea (corn earworm), Sylepta derogata (cotton leafroller), Pieris brassicae (cabbage white butterfly), Plutella xylostella (diabrotica moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta migratoria (acridium), Chortiocetes terminifera (acridium), Diabrotica spp. (root caterpillars), Panonychus ulmi (red mite), Panonychus citri (purple mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (common red spider mite), Phyllocoptruta oleivora (false rust mite), Polyphagotarsonemus latus (white mite), Brevipalpus spp.(flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blow flies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (e.g. Mastotermes spp.), the Kalotermitidae (e.g. Neotermes spp.), the Rhinotermitidae (e.g. Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis) and the Termitidae (e.g., Globitermes sulfureus). Petition 870200016293, dated 03 / 02 / 2020, pp. 63 / 92 54 / 77 Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh ant), Damalinia spp. and Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root-knot nematodes), Globodera spp. and Heterodera spp. (cyst-forming nematodes), Pratylenchus spp. (lesion-forming nematodes), Rhodopholus spp. (burrowing nematodes of bananas), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (ruminant nematode), Caenorhabditis elegans (vinegar eel worm), Trichostrongylus spp. (gastrointestinal nematodes), and Deroceras reticulatum (slug).
[0078] The compound of formula I and mixtures of the invention can be used for pest control in various plants, including soybeans (e.g., in some cases 10-70 g / ha), maize (e.g., in some cases 10-70 g / ha), sugarcane (e.g., in some cases 20-200 g / ha), alfalfa (e.g., in some cases 10-70 g / ha), brassicas (e.g., in some cases 10-50 g / ha), rapeseed (e.g., canola) (e.g., in some cases 20-70 g / ha), potatoes (including sweet potatoes) (e.g., in some cases 10-70 g / ha), cotton (e.g., in some cases 10-70 g / ha), rice (e.g., in some cases 10-70 g / ha), coffee (e.g., in some cases 30-150 g / ha), citrus (e.g., in some cases 60-200 g / ha), almonds (for example, in some cases 40-180 g / ha), fruits of vegetables, cucurbits and legumes (for example, tomatoes, bell peppers, chili peppers, eggplant, cucumber, pumpkin, etc.).) (e.g., in some cases 10-80 g / ha), tea (e.g., in some cases 20-150 g / ha), bulb vegetables (e.g., onions, leeks, etc.) (e.g., in some cases 30-90 g / ha), grapes (e.g., in some cases 30-180 g / ha), pome fruits (e.g., apples, pears, etc.) (e.g., in some cases 30-180 g / ha), and stone fruits (e.g., pears, plums, etc.) (e.g., in some cases 30-180 g / ha).
[0079] The mixtures of the invention can be used for pest control in various plants, including soybeans, corn, sugarcane, alfalfa, brassicas, rapeseed (e.g., canola), potatoes (including sweet potatoes), cotton, rice, Petition 870200016293, dated 03 / 02 / 2020, pp. 64 / 92 55 / 77 coffee, citrus fruits, almonds, vegetables, cucurbits and legumes (e.g., tomatoes, bell peppers, chili peppers, eggplant, cucumber, pumpkin, etc.), tea, bulb vegetables (e.g., onions, leeks, etc.), grapes, pome fruits (e.g., apples, pears, etc.), and stone fruits (e.g., pears, plums, etc.), and cereals.
[0080] The mixtures of the invention can be used in soybeans to control, for example, Elasmopalpus lignosellus, Diloboderus abderus, Diabrotica speciosa, Trialeurodes spp., Bemisia spp., aphids, Sternechus subsignatus, Formicidae, Agrotis ypsilon, Julus spp., Murgantia spp., Halyomorpha spp., Thyanta spp., Megascelis ssp., Procornitermes ssp., Gryllotalpidae, Nezara viridula, Piezodorus spp., Acrosternum spp., Neomegalotomus spp., Cerotoma trifurcata, Popillia japonica, Edessa spp., Liogenys fuscus, Euschistus heros, stem borer, Scaptocoris castanea, phyllophaga spp., Migdolus spp., Pseudoplusia includens, Anticarsia gemmatalis, Epinotia spp., Rachiplusia spp., Spodoptera spp., Bemisia tabaci, Tetranychus spp., Agriotes spp., Euschistus spp. The mixtures of the invention are preferably used in soybeans to control Diloboderus abderus, Diabrotica speciosa, Trialeurodes spp., Bemisia spp., Nezara viridula, Piezodorus spp., Acrosternum spp., Cerotoma trifurcata, Popillia japonica, Euschistus heros, Scaptocoris castanea, Phyllophaga spp., Migdolus spp., Agriotes spp., Euschistus spp.
[0081] The mixtures of the invention can be used in corn to control, for example, Euschistus heros, Euschistus spp., Dichelops furcatus, Diloboderus abderus, Thyanta spp., Elasmopalpus lignosellus, Halyomorpha spp., Spodoptera frugiperda, Nezara viridula, Cerotoma trifurcata, Popillia japonica, Agrotis ypsilon, Diabrotica speciosa, aphids, Heteroptera, Procornitermes spp., Scaptocoris castanea, Formicidae, Julus ssp., Dalbulus maidis, Diabrotica virgifera, Diabrotica spp., Mocis latipes, Bemisia tabaci, heliothis spp., Tetranychus spp., thrips spp., phyllophaga spp., Migdolus spp., scaptocoris spp., Liogenys fuscus, Spodoptera spp., Ostrinia spp., Sesamia spp., fireflies, Agriotes spp., Halotydeus destructor. As misturas da invenção are preferably used Petition 870200016293, dated 02 / 03 / 2020, p. 65 / 92 56 / 77 in corn to control Euschistus heros, Euschistus spp., Dichelops furcatus, Diloboderus abderus, Nezara viridula, Cerotoma trifurcata, Popillia japonica, Diabrotica speciosa, Diabrotica virgifera, Diabrotica spp., Tetranychus spp., Thrips spp., Phyllophaga spp., Migdolus spp., Scaptocoris spp., Agriotes spp..
[0082] The mixtures of the invention can be used in sugarcane to control, for example, Sphenophorus spp., termites, Migdolus spp., Diloboderus spp., Telchin licus, Diatrea saccharalis, Mahanarva spp., scale insects.
[0083] The mixtures of the invention can be used on alfalfa to control, for example, Hypera brunneipennis, Hypera postica, Colias eurytheme, Collops spp., Empoasca solana, Epitrix spp., Geocoris spp., Lygus hesperus, Lygus lineolaris, Spissistilus spp., Spodoptera spp., Aphids, Trichoplusia ni. The mixtures of the invention are preferably used on alfalfa to control Hypera brunneipennis, Hypera postica, Empoasca solana, Epitrix spp., Lygus hesperus, Lygus lineolaris, Trichoplusia ni.
[0084] The mixtures of the invention can be used in brassicas to control, for example, Plutella xylostella, Pieris spp., Mamestra spp., Plusia spp., Trichoplusia ni, Phyllotreta spp., Spodoptera spp., Empoasca spp., Thrips spp., Delia spp., Murgantia spp., Trialeurodes spp., Bemisia spp., Microtheca spp., and aphids. The mixtures of the invention are preferably used in brassicas to control Plutella xylostella, Pieris spp., Plusia spp., Trichoplusia ni, Phyllotreta spp., and Thrips spp.
[0085] The mixtures of the invention can be used in rapeseed, for example, canola, to control, for example, Meligethes spp., Ceutorhynchus napi, Halotydeus destructor, Psylloides spp..
[0086] The mixtures of the invention can be used on potatoes, including sweet potatoes, to control, for example, Empoasca spp., Leptinotarsa spp., Diabrotica speciosa, Phthorimaea spp., Paratrioza spp., Maladera matrida, Agriotes spp., aphids, fireflies. The mixtures of the invention are preferably used on potatoes, including sweet potatoes, to control Empoasca spp., Leptinotarsa spp., Diabrotica speciosa, Phthorimaea spp., Paratrioza spp., Petition 870200016293, dated 03 / 02 / 2020, pages 66 / 92 57 / 77 Agriotes spp.
[0087] The mixtures of the invention can be used on cotton to control, for example, Anthonomus grandis, Pectinophora spp., Heliothis spp., Spodoptera spp., Tetranychus spp., Empoasca spp., Thrips spp., Bemisia tabaci, Trialeurodes spp., Aphids, Lygus spp., Phyllophaga spp., Scaptocoris spp., Austroasca viridigrisea, Creontiades spp., Nezara spp., Piezodorus spp., Halotydeus destructor, Oxycaraenus hyalinipennis, Dysdercus cingulatus. The mixtures of the invention are preferably used in cotton to control Anthonomus grandis, Tetranychus spp., Empoasca spp., thrips spp., Lygus spp., phyllophaga spp., and Scaptocoris spp.
[0088] The mixtures of the invention can be used in rice to control, for example, Leptocorisa spp., Cnaphalocrosis spp., Chilo spp., Scirpophaga spp., Lissorhoptrus spp., Oebalus pugnax, Scotinophara spp., Nephotettix malayanus, Nephotettix nigropictus, Nephotettix parvus, Nephottetix virescens, Nephotettix spp., Conchonilhas, Sogatella furcifera, Nilaparvata lugens, Orseolia spp., Cnaphalocrocis medinalis, Marasmia spp., Stenchaetothrips biformis, Thrips spp., Hydrellia philippina, Grasshoppers, Pomacea canaliculata, Scirpophaga innotata, Chilo suppressalis, Chilo auricilius, Chilo polychrysus, Sesamia inferens, Laodelphax striatellus, Nymphula depunctalis, Oulema oryzae, Bed bugs. The mixtures of the invention are preferably used in rice to control Leptocorisa spp., Lissorhoptrus spp., Oebalus pugnax, Nephotettix malayanus, Nephotettix nigropictus, Nephotettix parvus, Nephottetix virescens, Nephotettix spp., Sogatella furcifera, Stenchaetothrips biformis, Thrips spp., Hydrellia philippina, Locusts, Pomacea canaliculata, Scirpophaga innotata, Chilo suppressalis, Chilo polychrysus, Oulema oryzae.
[0089] The mixtures of the invention can be used in coffee to control, for example, Hypothenemus Hampei, Perileucoptera Coffeella, Tetranychus spp., Brevipalpus spp., and scale insects. The mixtures of the invention are preferably used in coffee to control Hypothenemus Hampei and Perileucoptera Coffeella. Petition 870200016293, dated 03 / 02 / 2020, pp. 67 / 92 58 / 77
[0090] The mixtures of the invention can be used in citrus to control, for example, Panonychus citri, Phyllocoptruta oleivora, Brevipalpus spp., Diaphorina citri, Scirtothrips spp., Thrips spp., Unaspis spp., Ceratitis capitata, Phyllocnistis spp., Aphids, Hard Scales, Soft Scales, Mealybugs. The mixtures of the invention are preferably used in citrus to control Panonychus citri, Phyllocoptruta oleivora, Brevipalpus spp., Diaphorina citri, Scirtothrips spp., Thrips spp., Phyllocnistis spp.
[0091] The mixtures of the invention can be used in almonds to control, for example, Amyelois transitella, Tetranychus spp..
[0092] The mixtures of the invention can be used on fruits of vegetables, cucurbits and legumes, including tomatoes, peppers, chili peppers, eggplant, cucumbers, pumpkins, etc., to control, for example, Thrips spp., Tetranychus spp., Polyphagotarsonemus spp., Aculops spp., Empoasca spp., Spodoptera spp., Heliothis spp., Tuta absoluta, Liriomyza spp., Bemisia tabaci, Trialeurodes spp., Aphids, Paratrioza spp., Frankliniella occidentalis, Frankliniella spp., Anthonomus spp., Phyllotreta spp., Amrasca spp., Epilachna spp., Halyomorpha spp., Scirtothrips spp., Leucinodes spp., Neoleucinodes spp., Maruca spp., Fruit flies, Stink bugs, Lepidoptera, Coleoptera. The mixtures of the invention are preferably used on fruits of vegetables, cucurbits and legumes, including tomatoes, peppers, chili peppers, eggplant, cucumber, pumpkins, etc., to control Thrips spp., Tetranychus spp., Polyphagotarsonemus spp., Aculops spp., Empoasca spp., Spodoptera spp., Heliothis spp., Tuta absolute, Liriomyza spp., Paratrioza spp., Frankliniella occidentalis, Frankliniella spp., Amrasca spp., Scirtothrips spp., Leucinodes spp., Neoleucinodes spp.
[0093] The mixtures of the invention can be used in tea to control, for example, Pseudaulacaspis spp., Empoasca spp., Scirtothrips spp., Caloptilia theivora, Tetranychus spp. The mixtures of the invention are preferably used in tea to control Empoasca spp., Scirtothrips spp.
[0094] The mixtures of the invention can be used on bulbous vegetables, Petition 870200016293, dated 03 / 02 / 2020, pp. 68 / 92 59 / 77 including onions, leeks, etc., to control, for example, Thrips spp., Spodoptera spp., Heliothis spp. The mixtures of the invention are preferably used on bulb vegetables, including onions, leeks, etc., to control Thrips spp.
[0095] The mixtures of the invention can be used on grapes to control, for example, Empoasca spp., Lobesia spp., Eupoecilia ambiguella, Frankliniella spp., Thrips spp., Tetranychus spp., Rhipiphorothrips Cruentatus, Eotetranychus Willamettei, Erythroneura Elegantula, Scaphoides spp., Scelodonta strigicollis, and scale insects. The mixtures of the invention are preferably used on grapes to control Frankliniella spp., Thrips spp., Tetranychus spp., Rhipiphorothrips Cruentatus, and Scaphoides spp.
[0096] The mixtures of the invention can be used on pome fruits, including apples, pears, etc., to control, for example, Cacopsylla spp., Psylla spp., Panonychus ulmi, Cydia pomonella, Lepidoptera, Aphids, Hard Scales, Soft Scales. The mixtures of the invention are preferably used on pome fruits, including apples, pears, etc., to control Cacopsylla spp., Psylla spp., Panonychus ulmi.
[0097] The mixtures of the invention can be used on stone fruits to control, for example, Grapholita molesta, Scirtothrips spp., Thrips spp., Frankliniella spp., Tetranychus spp., Aphids, Hard Scales, Soft Scales, Mealybugs. The mixtures of the invention are preferably used on stone fruits to control Scirtothrips spp., Thrips spp., Frankliniella spp., Tetranychus spp.
[0098] The mixtures of the invention can be used in cereals to control, for example, Aphids, Stink bugs, ground mites, Eurygaster integriceps, Zabrus tenebrioides, Anisoplia austriaca, Chaetocnema aridula, Phyllotreta spp., Oulema melanopus, Oscinella spp., Delia spp., Mayetiola spp., Contarinia spp., Cephus spp., Steneotarsonemus spp., Apamea spp..
[0099] In another embodiment, the compounds of formula I and mixtures of the invention can be used in rice to control Baliothrips biformis (Thrips), Petition 870200016293, dated 03 / 02 / 2020, pp. 69 / 92 60 / 77 Chilo spp. (e.g., Chilo polychrysus (Dark-headed striped borer), Chilo suppressalis (Rice stem borer), Chilo indicus (Rice stem borer with husk), Chilo polychrysus (Dark-headed rice borer), Chilo suppressalis (Striped stem borer)), Cnaphalocrocis medinalis (Rice leaf bender), Dicladispa armigera (Hispa), Hydrellia philipina (Rice spiral larva), Laodelphax spp. (Smaller brown fulgoromorph) (e.g., Laodelphax striatellus), Lema oryzae (Rice leaf beetle), Leptocorsia acuta (Rice stink bug), Leptocorsia oratorius (Rice stink bug), Lissorhoptrus oryzophilus (Rice water weevil), Mythemina separata (Grain caterpillar), Nephottetix spp.(Green Cigar) (for example, Nephotettix cincticeps, Nephotettix malayanus, Nephotettix nigropictus, Nephotettix parvus, Nephottetix virescens), Nilaparvata lugens (Brown Fulgoromorph), Nymphula depunctalis (Rice borer), Orseolia oryzae (Rice mosquito), Oulema oryzae (Rice mosquito), Scirpophaga incertulas (Yellow stem borer), Scirpophaga innotata (White stem borer), Scotinophara coarctata (Black rice borer), Sogaella frucifera (White-backed Fulgoromorph), Steneotarsonemus spinki.
[00100] The compounds of formula I and mixtures of the invention can be used to control pests of domestic animals including: Ants, Bedbugs (adults), Bees, Beetles, Woodlice, Carpenter Bees, Carpet Beetles, Centipedes, Cicadas, Beetles, Mites, Cockroaches, Flour Weevils, Crickets, Earwigs, Firebugs, Fleas, Flies, Smaller Grain Borers, Millipedes, Mosquitoes, Red Flour Beetles, Rice Weevils, Serrated Grain Beetles, Moths, Woodlice, Spiders, Termites, Ticks, Wasps, Cockroaches, Crickets, Flies, Maca Beetles (such as Darkling, Hide, and Carrion), Mosquitoes, Armadillo, Scorpions, Spiders, Mites (Spotted, Fir), Ticks.
[00101] The compounds of formula I and mixtures of the invention can be used to control pests of ornamental plants including: Ants (Including imported fire ants), Cereal caterpillars, Aza caterpillars Petition 870200016293, dated 03 / 02 / 2020, pp. 70 / 92 61 / 77 lea, Aphids, Sack worms, Black vine beetles (adult), Negundo worms, Budworms, California woodworms, Worms, Cockroaches, Crickets, Caterpillars, Oriental tent caterpillars, Elm leaf beetles, European hornets, Autumn spiders, Flea beetles, Forest tent caterpillars, Gypsy moth larvae, Japanese beetles (adults), June beetles (adults), Lace worms, Leaf-feeding caterpillars, Leafhoppers, Leaf miners (adults), Moths, Leaf skeletonizers, Cecidomyidia, Mosquitoes, Oliander moth larvae, Pine sawdust flies, Pine shoot beetle, Pine tip moths, Worms, Plant worms, Root weevils, Flies From sawdust, scale insects (crawling), spiders, leafhoppers, striped beetles, striped woodworms, thrips, moths, Tussock moth larvae, wasps, large mites, brown bugs, California bugs (crawling), clover mites, scale insects.Pine needle insects (crawling insects), spider mites, whiteflies.
[00102] The compounds of formula I and mixtures of the invention can be used to control grass pests including: Ants (Including imported fire ants, Cereal caterpillars, Centipedes, Crickets, Caterpillars, Earwigs, Fleas (adult), Grasshoppers, Japanese beetles (adult), Millipedes, Mites, Mosquitoes (adult), Worms, Lawn worms, Insects, Ticks (including species that transmit Lyme disease), Bluegrass worms (adult), Blackgrass Ataenius (adult), Larvae, Fleas (adult), Larvae (suppression), Hyperodes weevils (adult), Crickets (nymphs and young adults), Crickets (mature adults), Bed bugs.
[00103] The compounds of formula (I) and mixture of the invention, in particular those in the tables above, can be used for soil applications, including as a seed application, to target at least the following: sucking pests such as aphids, thrips, brown leafhopper (e.g., in rice), biting insects, whiteflies (e.g., in cotton and legumes), mites; in soil pests such as corn rootworms, Petition 870200016293, dated 03 / 02 / 2020, pp. 71 / 92 62 / 77 fireflies, white grubs, zabrus, termites (e.g., in sugarcane, soybeans, pasture), worms, cabbage root fly, red-legged earth mite; in lepidoptera, such as spodoptera, worms, elasmopalpus, plutella (e.g., brassica), stem borers, leaf miners, flea beetle, Sternechus; in nematicides, such as Heterodera glycines (e.g., in soybeans), Pratylenchus brachyurus (e.g., in maize), P. zeae (e.g., in maize), P. penetrans (e.g., in maize), Meloidogyne incognita (e.g., in legumes), Heterodera schachtii (e.g., in sugar beets), Rotylenchus reniformis (e.g., in cotton), Heterodera avenae (e.g., in cereals), Pratylenchus neglectus (e.g., in cereals), thornei (e.g., in cereals).
[00104] The compounds of formula (I) and mixture of the invention, in particular those in the tables above, can be used for seed applications at least in the following: groundworms for corn, soybean, sugarcane: Migdolus spp; Phyllophaga spp.; Diloboderus spp; Cyclocephala spp; Lyogenys fuscus; sugarcane weevils: Sphenophorus levis & Metamasius hemipterus; termites for soybean, sugarcane, pasture, others: Heterotermes tenuis; Heterotermes longiceps; Cornitermes cumulans; Procornitermes triacifer; Neocapritermes opacus; Neocapritermes parvus; corn rootworms for corn and potato: Diabrotica spp., Seedworm: Delia platura; Soil bugs: Scaptocoris castanea; fireflies: Agriotes spp; Athous spp; Hypnodes bicolor; Ctenicera destructor; Limonius canu; Limonius californicus; rice water weevil: Lissorhoptrus oryzophilus; red-legged earth mite: Halotydeus destructor.
[00105] For soil applications using compounds of formula I in sugarcane, including application to sugarcane propagation material such as shoots, the following mixing partners are of particular interest: selected neonicotinoid insecticides, in particular thiamethoxam, imidacloprid and clothianidin, sulfoxaflor, abamectin, carbofuran, tefluthrin, fipronil, etiprole, spinosad, lambda-cyhalothrin, bisamides, in particular chlorantraniliprole, Petition 870200016293, dated 03 / 02 / 2020, pp. 72 / 92 63 / 77 cyantraniliprole, flubendiamide; optionally with selected fungicides of azoxystrobin, cyproconazole, thiabendazole, fluazinam, fludioxonil, mefenoxam, sedaxan. For foliar applications using compounds of formula I in sugarcane, the following mixing partners are of particular interest: selected insecticides of thiamethoxam, lambda-cyhalothrin, spirotetramat, spinetoran, chlorantraniliprole, lufenuron; optionally with selected fungicides of N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide [CAS 1072957-71-1], azoxystrobin, cyproconazole, prothioconazole. Combinations with glyphosate are also of interest.
[00106] Particular combinations of interest for sugarcane, particularly in sugarcane propagation material such as shoots, include a compound of formula I with thiamethoxam and abamectin, a compound of formula I with thiamethoxam and cyantraniliprole, a compound of formula I with thiamethoxam and chlorantraniliprole.Additional combinations of particular interest for sugarcane include a compound of the formula I + thiamethoxam + abamectin + mefenoxam + fludioxonil + azoxystrobin + thiabendazole; A compound of the formula I + abamectin + mefenoxam + fludioxonil + azoxystrobin + thiabendazole, a compound of the formula I + thiamethoxam + mefenoxam + fludioxonil + azoxystrobin + thiabendazole, a compound of the formula I + thiamethoxam + abamectin + mefenoxam + fludioxonil + azoxystrobin + thiabendazole, a compound of the formula I + thiamethoxam + abamectin + fludioxonil + azoxystrobin + thiabendazole, a compound of the formula I + thiamethoxam + abamectin + mefenoxam + azoxystrobin + thiabendazole, a compound of the formula I + thiamethoxam + abamectin + mefenoxam + fludioxonil + thiabendazole, a compound of the formula I + thiamethoxam + abamectin + mefenoxam + fludioxonil + thiabendazole. Examples of ratios are below.
[00107] The amount of a combination of the invention to be applied will depend on several factors, such as the compounds employed; the subject of the treatment, such as, for example, plants, soil or seeds; the type of treatment Petition 870200016293, dated 03 / 02 / 2020, pp. 73 / 92 64 / 77 ment, such as, for example, spraying, dusting or seed treatment; the purpose of the treatment, such as, for example, prophylactic or therapeutic; the type of pest to be controlled or the time of application.
[00108] Mixtures comprising a compound of formula I, for example, those selected from Table A, and one or more active ingredients as described above may be applied, for example, in a single ready-mix form, in a combined spray mixture composed of separate formulations of the individual active ingredient components, such as a tank mix, and in a combined use of the individual active ingredients when applied in a sequential manner, i.e., one after the other with a relatively short period of time, such as a few hours or days. The order of application of the compounds of formula I selected from Table A and the active ingredients as described above is not essential for carrying out the present invention.
[00109] The synergistic activity of the combination is apparent from the fact that the pesticidal activity of the A + B composition is greater than the sum of the pesticidal activities of A and B.
[00110] The method of the invention comprises applying to useful plants, their locus or their propagation material, in a mixture or separately, a synergistically effective aggregate quantity of a component A and a component B.
[00111] Some of the compositions described in the invention have a systemic action and can be used as foliar, soil and seed treatment pesticides.
[00112] With the combinations according to the invention, it is possible to inhibit or destroy pests that occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) in different useful plants, while at the same time the plant parts that grow later are also protected from pest attack.
[00113] It is understood that the compounds of formula I represent a new Petition 870200016293, dated 03 / 02 / 2020, pp. 74 / 92 65 / 77 mode of action. Accordingly, it can be noted that compounds of formula I can be used to control mites, insects and nematodes, preferably insects, that are resistant to active ingredients having other modes of action, for example, they can be included in resistance management programs.
[00114] The combinations of the present invention are of particular interest for pest control in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugar beets, and wheat, rye, barley, oats, rice, corn, lawns, cotton, soybeans, rapeseed, legume crops, sunflower, coffee, sugarcane, fruits and ornamental plants in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.
[00115] The combinations according to the invention are applied by treating pests, useful plants, their locus, their propagation material, natural substances of plant and / or animal origin that have been taken from the natural life cycle, and / or their processed forms, or industrial materials threatened by pest attack, with a combination of components A and B in a synergistically effective quantity.
[00116] The combinations according to the invention can be applied before or after the infection or contamination of useful plants, their propagation material, natural substances of plant and / or animal origin, which have been taken from the natural life cycle, and / or their processed forms, or industrial materials by pests.
[00117] The combinations according to the invention can be used to control, that is, contain or destroy, pests of the above-mentioned type that occur in plants useful in agriculture, horticulture and forestry, or in organs of useful plants, such as fruits, flowers, foliage, cuttings, tubers or roots, and in some cases even in organs of useful plants that are formed at a later time remain protected against these pests. Petition 870200016293, dated 03 / 02 / 2020, pp. 75 / 92 66 / 77
[00118] When applied to useful plants, the compound of formula I is generally applied at a rate of 1 to 500 g ai / ha in association with 1 to 2000 g ai / ha of a compound of component B, depending on the class of chemical product employed as component B.
[00119] Generally, for plant propagation material, such as seed treatment, application rates can vary from 0.001 to 10 g / kg of seeds of the active ingredients. When the combinations of the present invention are used for seed treatment, rates of 0.001 to 5 g of a compound of formula I per kg of seeds, preferably from 0.01 to 1 g per kg of seeds, and 0.001 to 5 g of a compound of component B, per kg of seeds, preferably from 0.01 to 1 g per kg of seeds, are generally sufficient.
[00120] The weight ratio of A to B can generally be between 1000:1 and 1:1000. In other embodiments, this weight ratio of A to B can be between 500:1 and 1:500, for example, between 100:1 and 1:100, for example, between 1:50 and 50:1, for example, 1:20 and 20:1. Other embodiments of component (B) in relation to component (A) vary from 500:1 to 1:250, with one embodiment being from 200:1 to 1:150, another embodiment being from 150:1 to 1:50 and another embodiment being from 50:1 to 1:10. Also noteworthy are the weight ratios of component (B) to component (A) which vary from 450:1 to 1:300, with one modality being from 150:1 to 1:100, another modality from 30:1 to 1:25 and another modality from 10:1 to 1:10. Other modalities include 1:5 to 5:1, for example 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5.
[00121] The invention also provides pesticide mixtures comprising a combination of components A and B as mentioned above in a synergistically effective amount, together with an agriculturally acceptable carrier, and optionally a surfactant.
[00122] Spodoptera preferably means Spodoptera littoralis. Heliothis preferably means Heliothis virescens. Tetranychus preferably means Tetranychus urticae. Petition 870200016293, dated 03 / 02 / 2020, pp. 76 / 92 67 / 77
[00123] The compositions of the invention can be employed in any conventional form, for example in the form of a double package, a dry seed treatment powder (DS), a seed treatment emulsion (ES), a flowable seed treatment concentrate (FS) (for example, with a high concentration of active ingredient), a seed treatment solution (LS), a water-dispersible seed treatment powder (WS), a seed treatment capsule suspension (CF), a seed treatment gel (GF), an emulsifiable concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water-dispersible granule (WG), an emulsifiable granule (EG), a water-in-oil emulsion (EO), an oil-in-water emulsion (EW), a microemulsion (ME), an oil dispersion (OD), an oil-miscible fluid (OF), an oil-miscible liquid (OL), a soluble concentrate (SL), a suspension of ultra-low volume (SU),an ultra-low volume (UL) liquid, a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG), or any technically practicable formulation in combination with agriculturally acceptable adjuvants.
[00124] Such compositions may be produced conventionally, for example, by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulation ingredients such as surfactants, biocides, antifreeze, adhesives, thickeners and compounds that provide adjuvant effects). Similarly, conventional slow-release formulations may be employed if long-lasting efficacy is desired. In particular, formulations to be applied in spray 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 adjuvant effects, for example, the condensation product of formaldehyde with naphthalene sulfonate, an alkylaryl sulfonate, a lignin sulfonate, a fatty alkyl sulfate, and alkyl Petition 870200016293, dated 03 / 02 / 2020, pp. 77 / 92 68 / 77 ethoxylated phenol and an ethoxylated fatty alcohol.
[00125] A seed treatment formulation is applied in a manner known per se to seeds using the combination of the invention and a diluent in a suitable seed treatment form, for example, as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed treatment formulations are known in the art. The seed treatment formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, for example, as slow-release capsules or microcapsules.A typical tank-mix formulation for seed treatment application comprises 0.25 to 80%, especially 1 to 75%, of the desired ingredients, and 99.75 to 20%, especially 99 to 25%, of solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries may be a surfactant in an amount of 0 to 40%, especially 0.5 to 30%, based on the tank-mix formulation. A typical premix formulation for seed treatment application comprises 0.5 to 99.9%, especially 1 to 95%, of the desired ingredients, 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 may be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on the premix formulation.
[00126] Application rates for a plant propagation material treatment vary, for example, according to the type of use, type of crop, the specific compound(s) and / or agent(s) used, and type of plant propagation material. The appropriate rate is an amount effective to provide the desired action (such as disease or pest control) and can be determined by routine trials and experimentation known to a person skilled in the art.
[00127] Generally, for soil treatments, application rates can vary from 0.05 to 3 kg per hectare (g / ha) of ingredients. Generally Petition 870200016293, dated 03 / 02 / 2020, pp. 78 / 92 69 / 77 for seed treatments, application rates can vary from 0.5 to 1000 g / 100 kg of seed ingredients.
[00128] In general, formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% of an agriculturally acceptable surfactant, and 10 to 99.99% of solid or liquid formulation inerts and adjuvant(s), the active agent consisting at least of the compound of formula I together with a compound of component B, and optionally other active agents, particularly microbiocides or preservatives or the like. Concentrated forms of the compositions generally contain between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of the formulation may, for example, contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Although commercial products are preferably formulated as concentrates, the end user will normally employ diluted formulations. Formulation Examples Powders for dry seed treatment a) b) c) active ingredients 25% 50% 75% light mineral oil 5% 5% 5% highly dispersed silicic acid 5% 5% - Kaolin 65% 40% - Talc - 20
[00129] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, resulting in powders that can be used directly for seed treatment. Dusts a) b) c) Active ingredients 5% 6% 4% Talc 95% - - Kaolin - 94% - Mineral filler - - 96%
[00130] Ready-to-use powders are obtained by mixing the combination with the conveyor and grinding the mixture in a suitable mill. Such powders Petition 870200016293, dated 03 / 02 / 2020, pp. 79 / 92 70 / 77 can also be used for dry seed treatments. Suspension concentrate Active ingredients: 40% propylene glycol, 10% polyethylene glycol nonylphenol ether (15 moles of ethylene oxide), 6% sodium lignosulfonate, 10% carboxymethylcellulose, 1% silicone oil (in the form of a 75% emulsion in water), 1% water, 32%
[00131] The finely ground mixture is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, seeds can be treated and protected against infestation by spraying, pouring or soaking. Concentrate suitable for flowable application in seed treatment. Active ingredients: 40% propylene glycol, 5% butanol PO / EO copolymer, 2% Tristyrenephenol with 10-20 moles of EO, 2% 1,2-benzisothiazolin-3-one (as a 20% solution in water), 0.5% calcium salt of monoazo pigment, 5% silicone oil (as a 75% emulsion in water), 0.2% water, 45.3%
[00132] The finely ground mixture is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, seeds can be treated and protected against infestation by spraying, pouring or soaking.
[00133] The invention further relates to a product for use in agriculture and horticulture comprising a capsule in which at least one seed treated with the inventive compound is located. In another embodiment, the product comprises a capsule in which at least one seed, treated or untreated, and the inventive compound are located. Petition 870200016293, dated 03 / 02 / 2020, pages 80 / 92 71 / 77 Slow-Release Capsule Suspension
[00134] 28 parts of the inventive compound are mixed with 2 parts of an aromatic solvent and 7 parts of a diisocyanate / polymethylenepolyphenylisocyanate toluene mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts an antifoaming agent, and 51.6 parts water until the desired particle size is achieved. To this emulsion is added a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts water. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts a thickener and 3 parts a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The average capsule diameter is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a suitable device. Examples
[00135] The Examples in PCT / EP2010 / 068605, incorporated herein by reference, demonstrate that the compounds of formula I have insecticidal activity.
[00136] A synergistic effect exists whenever the action of a combination of active ingredients is greater than the sum of the actions of the individual components.
[00137] The expected action E for a given combination of active ingredients follows the so-called COLBY formula and can be calculated as follows (COLBY, SR. Calculating synergistic and antagonistic responses of herbicide combination. Weeds, Vol. 15, pages 20-22; 1967): ppm = milligrams of active ingredient (i.e., active ingredient) per liter of spray mixture X = % of action per active ingredient A) using p ppm of active ingredient Y = % of action per active ingredient B) using q ppm of active ingredient. According to COLBY, the expected (additive) action of the active ingredients X · Y vos A)+B) using p+q ppm of active ingredient is E = X + Y
[00138] If the actually observed action (O) is greater than the expected action Petition 870200016293, dated 03 / 02 / 2020, pages 81 / 92 72 / 77 expected (E), then the action of the combination is superadditive, that is, a synergistic effect occurred. In mathematical terms, the synergy factor SF corresponds to O / E. In agricultural practice, an SF of > 1.2 indicates a significant improvement relative to the purely complementary addition of activities (expected activity), while an SF of < 0.9 in routine practical application indicates a loss of activity compared to the expected activity.
[00139] Tables 1 to 3 show mixtures of the present invention demonstrating remarkable synergistic effects. Since the mortality percentage cannot exceed 100%, the unexpected increase in insecticidal activity can only be greater when the separate active ingredient components alone are at application rates providing considerably less than 100% control. The synergy may not be evident at low application rates where the individual active ingredient components alone have low activity. However, in some cases, high activity was observed for combinations where the individual active ingredient alone at the same application rate had essentially no activity. The synergism is remarkable. Tetranychus urticae (Two-spotted spider mite) (contact / feeding activity)
[00140] Bean plants are infested with populations of mites of mixed ages. 1 day after infestation, the plants are treated in a spray chamber with diluted test solutions. 1 and 8 days later, the samples are checked for adult mortality. Two replicates were evaluated per treatment. Petition 870200016293, dated 03 / 02 / 2020, pages 82 / 92 73 / 77 difference +5 o +25 +50 +25 +25 % of expected control o 00 o M- 40 ooo % of observed control of A58 + TMX LO 00 o M- 65 o LO 25 25 % of observed control of TMX ooo O oo % of observed control of A58 o 00 o M- o M- ooo Application ppm 0.4 + 200 0.2 + 200 0.2 + 100 0.1 + 400 0.1 + 200 0.1 + 50 A58 + TMX A58 + TMX A58 + TMX A58 + TMX A58 + TMX A58 + TMX CM Cü Φ -Q Ass Ass difference 1 + 15 + 7 o + 10 + 10 % of expected control 96 LO 00 00 00 95 LO 00 80 % of observed control of A58 + LCYH 95 100 95 95 95 06 % of observed control of LCYH 08 75 08 95 LO 00 08 % of observed control of A58 08 o M- o M- ooo Application ppm 0.4 + 25 0.2 + 12.5 0.2 + 25 0.1 + 100 0.1 + 50 0.1 + 25 A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH Petition 870200016293, dated 03 / 02 / 2020, pages 83 / 92 74 / 77 difference + 15 +35 + 10 +5 +75 o +50 +5 + 10 +35 +55 +25 o +50 +65 +45 + 15 + 15 +30 % of expected control 75 25 LO 00 80 o 75 25 80 75 25 oo 75 25 ooooo % of observed control of A58 + LCYH 06 09 95 LO 00 75 75 75 LO 00 LO 00 09 55 25 65 45 15 15 08 % of observed control of LCYH 75 25 LO 00 08 o 75 25 08 75 25 oo 75 25 ooooo % of observed control of A58 ooooooooooooooooooo Application ppm 0.1 + 12.5 0.1 + 6.25 0.05 + 50 0.05 + 25 0.05 + 3.125 0.05 + 12.5 0.05 + 6.25 0.025 + 25 0.025 + 12.5 0.025 + 6.25 0.025 + 3.125 0.025 + 1.562 0.0125 + 12.5 0.0125 + 6.25 0.0125 + 3.125 0.0062 + 1.562 0.0062 + 3.125 0.0031 + 1.562 0.0031 + 0.781 A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH A58 + LCYH Petition 870200016293, dated 03 / 02 / 2020, pages 84 / 92 75 / 77 Difference in expected control percentage: 25% observed control percentage of A58 + LCYH; 25% observed control percentage of LCYH; 25% observed control percentage of A58. Application ppm: 0.006 + 6.25 A58 + LCYH ω φ co LO ro sz op Cü ω 05 o ω o And ooo difference -4.25 00 1 +6 -15 +15 o -5 o CM + +45 +40 O X1 +15 % of expected control 99.25 98 84 95 09 25 95 09 25 o 95 09 % of observed control of A58 + DFN 95 06 06 08 75 25 06 08 oo LO CO 75 % of observed control of DFN 95 95 09 95 09 25 95 09 25 o 95 09 % of observed control of A58 85 09 09 ooooooooo Application ppm 0.4 + 25 0.2 + 25 0.2 + 12.5 0.1 + 25 0.1 + 12.5 0.1 + 6.25 0.05 + 25 0.05 + 12.5 0.05 + 6.25 0.05 + 3.125 0.025 + 25 0.025 + 12.5 A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN Petition 870200016293, dated 03 / 02 / 2020, pages 85 / 92 76 / 77 difference +10 +65 +25 or CM + +65 +25 +15 or +65 % of expected control 25 oo 09 25 oo 25 or % of observed control of A58 + DFN 35 65 25 08 06 25 15 25 65 % of observed control of DFN 25 oo 25 o % observed control of A58 ooooooooo Application ppm 0.025 + 6.25 0.025 + 3.125 0.025 + 1.562 0.0125 + 12.5 0.0125 + 6.25 0.0125 + 0.125 + 0.0125 1.562 0.0062 + 6.25 0.0062 + 3.125 A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN A58 + DFN Petition 870200016293, of 03 / 02 / 2020, p. 86 / 92 77 / 77
[00141] In the tables above, column 2 shows the application rates used, where the first rate given corresponds to the compound in column 3 and the second rate given corresponds to the compound in column 4. Columns 3 and 4 show the control observed from the compounds alone. Column 5 shows the control observed from the combined application of both compounds. Data are not shown for experiments where there was no insect mortality when the compounds were applied alone and in combination. When a compound applied alone did not give any control at a particular rate, it was assumed that lower rates of that compound alone would also not give any control.
Claims
1. Pesticide mixture characterized by comprising a component A and a component B, wherein component A is a compound of formula I and component B is lambda-cyhalothrin.
2. Pesticide mixture, according to claim 1, characterized in that component A is a mixture of compounds I* and I** wherein the molar ratio of compound I** compared to the total amount of both enantiomers is greater than 50%. Petition 870260041264, dated 04 / 05 / 2026, page 15 / 16 2 / 2 3. Pesticide mixture, according to claim 1 or 2, characterized in that the mixture comprises an agriculturally acceptable carrier and optionally a surfactant.
4. Pesticide mixture, according to any one of claims 1 to 3, characterized in that the weight ratio of A to B is 1000:1 to 1:1000.
5. A method for controlling insects, mites, nematodes, or mollusks, characterized by comprising applying a combination of components A and B to a pest, a locus of a pest, or a plant susceptible to attack by a pest, wherein components A and B are as defined in any one of claims 1 to 4.
6. Seed characterized by comprising a mixture as defined in any one of claims 1 to 5.
7. A method characterized by comprising coating a seed with a mixture as defined in any one of claims 1 to 5.