Pesticide complex

Abstract

The present invention relates to pesticidally active, in particular insecticidally active, compositions comprising thiamethoxam and their use for controlling animal pests in agricultural crops.

Description

Technical Field

[0001] The present invention relates to a composition comprising thiamethoxam which is pesticidally effective, especially insecticidally effective, and to its use for controlling animal pests in crops.

[0002] Pesticidal formulations comprising thiamethoxam are known, for example, from WO 01 / 20986. However, there is a continuing need to provide pesticidal compositions having any number of beneficial properties, especially an advantageous level of biological efficacy for protecting plants against insects, or excellent properties for use as an agrochemical active ingredient (e.g., high biological efficacy, advantageous activity spectrum, high safety profile (including improved crop tolerance), improved physicochemical properties, or high biodegradability).

[0003] It has now been found that further formulations comprising a specific combination of thiamethoxam and a surfactant provide excellent stability performance in aqueous compositions of thiamethoxam, especially in formulations comprising a flowable concentrate for seed treatment of thiamethoxam.

[0004] According to a first aspect of the present invention: (a) a compound of formula (I):

Chemical formula

[0005] For the purposes of the present invention, the pest-killing compositions according to the present invention are intended to cover all of their biologically equivalent compositions.

[0006] Surprisingly, the novel pest-killing compositions of the present invention have been found to exhibit long-term physical stability during storage, combined with excellent crystal growth inhibitory properties and a level of biological efficacy that is highly advantageous for controlling or preventing insect-induced plant damage. The pest-killing compositions of the present invention also unexpectedly exhibit good stability when diluted at application ratios.

[0007] Typically, the pest-killing compositions of the present invention: (a) Compound of formula (I): [ka] Or, its agriculturally acceptable salts, stereoisomers, enantiomers, tautomers, or N-oxides; (b) Water; (c) At least one block copolymer of ethylene oxide and propylene oxide of formula (II): HO-(CH2CH2O) x -(CH(CH3)CH2O) y -(CH2CH2O) x’ -H (wherein, x and x’ are equal to or different from each other and are integers from 70 to 120, y is an integer from 20 to 45, the polyoxyethylene:polyoxypropylene chain length ratio is from 4:1 to 7:1) and at least one alkoxylated lignosulfonate of formula (III):

Chemical formula

[0008] Typically, the water in the pest control composition of the present invention complements up to 100% by weight based on the total weight of the composition.

[0009] Surprisingly, it was also found that using at least one clay in combination with at least one heteropolysaccharide in the pest-killing composition of the present invention unexpectedly further helps prevent precipitate formation, and even if precipitate does form, it becomes easier to re-homogenize it.

[0010] Preferably, the pest-killing composition of the present invention: (a) 10% to 75% by weight of the compound of formula (I), or its phytochemically acceptable salts, stereoisomers, enantiomers, tautomers, or N-oxides, based on the total weight of the composition; (b) 10% to 65% by weight of water based on the total weight of the composition; (c) A surfactant system in an amount of 1% to 25% by weight, based on the total weight of the composition; (d) at least one type of clay in an amount of 0.1% to 2% by weight, based on the total weight of the composition; and (e) 0.05% to 1% by weight of at least one heteropolysaccharide based on the total weight of the composition Includes.

[0011] More preferably, the pest-killing composition of the present invention: (a) 25% to 60% by weight of the compound of formula (I), or its phytochemically acceptable salts, stereoisomers, enantiomers, tautomers, or N-oxides, based on the total weight of the composition; (b) 25% to 60% by weight of water based on the total weight of the composition; (c) A surfactant system in an amount of 2% to 15% by weight, based on the total weight of the composition; (d) at least one type of clay in an amount of 0.5% to 1.5% by weight, based on the total weight of the composition; and (e) 0.05% to 0.15% by weight of at least one heteropolysaccharide based on the total weight of the composition Includes.

[0012] More preferably, the pest-killing composition of the present invention: (a) 40% to 60% by weight of the compound of formula (I), or its phytochemically acceptable salts, stereoisomers, enantiomers, tautomers, or N-oxides, based on the total weight of the composition; (b) 30% to 50% by weight of water based on the total weight of the composition; (c) A surfactant system in an amount of 4% to 10% by weight, based on the total weight of the composition; (d) at least one type of clay in an amount of 0.08% to 1.2% by weight, based on the total weight of the composition; and (e) 0.06% to 0.15% by weight of at least one heteropolysaccharide based on the total weight of the composition Includes.

[0013] As used herein, the term "chain length ratio" refers to the oxyethylene unit, i.e., -(CH2CH2O) x -and-(CH2CH2O) x’ The total number of - units and oxypropylene units, i.e., -(CH(CH3)CH2O) y - represents the ratio of the total number of x, x', and y as defined above.

[0014] As used herein, the term "polyoxyethylene" means one or more polymer chains containing oxyethylene units.

[0015] As used herein, the term "polyoxypropylene" means one or more polymer chains containing oxypropylene units.

[0016] Preferably, in a block copolymer of ethylene oxide and propylene oxide of formula (II), x and x' are either equal to or different from each other, and are integers between 70 and 120, and y is an integer between 20 and 45. Here, the polyoxyethylene:polyoxypropylene chain length ratio is 4:1 to 6:1, preferably 5:1 to 6:1.

[0017] In embodiments of the present invention, in a block copolymer of ethylene oxide and propylene oxide of formula (II), x and x' are equal to each other, and are integers between 70 and 120, and y is an integer between 20 and 45. Here, the polyoxyethylene:polyoxypropylene chain length ratio is 4:1 to 6:1, preferably 5:1 to 6:1.

[0018] Preferred examples of the ethylene oxide and propylene oxide block copolymer of formula (II) according to this embodiment of the present invention are selected from the group consisting of the following. HO-(CH2CH2O) 80 -(CH(CH3)CH2O) 30 -(CH2CH2O) 80 -H; HO-(CH2CH2O) 97 -(CH(CH3)CH2O) 39 -(CH2CH2O) 97 -H; and HO-(CH2CH2O) 118 -(CH(CH3)CH2O) 45 -(CH2CH2O) 118 -H.

[0019] More preferably, in a block copolymer of ethylene oxide and propylene oxide of formula (II), x and x' are either equal to or different from each other, and are integers between 70 and 120, and y is an integer between 20 and 35. Here, the polyoxyethylene:polyoxypropylene chain length ratio is 4:1 to 6:1, preferably 5:1 to 6:1.

[0020] More preferably, in a block copolymer of ethylene oxide and propylene oxide of formula (II), x and x' are either equal to or different from each other, and are integers between 75 and 85, and y is an integer between 25 and 35. Here, the polyoxyethylene:polyoxypropylene chain length ratio is 5:1 to 6:1.

[0021] More preferably, in a block copolymer of ethylene oxide and propylene oxide of formula (II), x and x' are either equal to or different from each other, and are integers between 75 and 80, and y is an integer between 25 and 30. Here, the polyoxyethylene:polyoxypropylene chain length ratio is 5:1 to 6:1, preferably 5.1:1 to 5.5:1.

[0022] Non-limiting examples of ethylene oxide and propylene oxide block copolymers of formula (II) suitable for use in the pest-killing compositions of the present invention include, for example, surfactants commercially available under trade names PLURONIC® F68, PLURONIC® F88, and PLURONIC® F98.

[0023] Preferably, in the alkoxylated lignosulfonate of formula (III), R 1 , R 2 and R 3 If any of them is -CH2CH2, then i, j, and k are equal to or different from each other, and are integers between 1 and 12, preferably 1 and 4, more preferably 1 and 3, or R 1 , R 2 and R 3 If any of them is -CH(CH3)CH2, then i, j, and k are equal to or different from each other, and are integers from 1 to 6, preferably 1 to 3, more preferably 1 to 2, or R 1 , R 2 and R 3 If any of them is -CH2CH2CH2CH2-, then i, j, and k are equal to or different from each other and are integers between 1 and 3, preferably between 1 and 2, more preferably 1. Here, R 1 , R 2and R 3 They are either equal to or different from each other.

[0024] Preferably, X in the alkoxylated lignosulfonate of formula (III) is sodium.

[0025] Preferably, the alkoxylated lignosulfonate of formula (III) has a degree of sulfonation of 0.5 to 1.5 mol / kg, preferably 0.7 to 1.2 mol / kg.

[0026] Non-limiting examples of alkoxylated lignosulfonates of formula (III) suitable for use in the pest-killing compositions of the present invention include, for example, a surfactant commercially available under the trade name REAX® 1425E.

[0027] Preferably, the surfactant system is: Based on the total weight of the surfactant system, 20% to 45% by weight of at least one polyoxyethylene-polyoxypropylene block copolymer of formula (II); and Based on the total weight of the surfactant system, 55% to 80% by weight of at least one alkoxylated lignosulfonate of formula (III) is required. Includes.

[0028] More preferably, the surfactant system is: Based on the total weight of the surfactant system, 30% to 40% by weight of at least one polyoxyethylene-polyoxypropylene block copolymer of formula (II); and Based on the total weight of the surfactant system, 60% to 70% by weight of at least one alkoxylated lignosulfonate of formula (III) is required. Includes.

[0029] More preferably, the surfactant system is: Based on the total weight of the surfactant system, 35% to 40% by weight of at least one polyoxyethylene-polyoxypropylene block copolymer of formula (II); and Based on the total weight of the surfactant system, 60% to 65% by weight of at least one alkoxylated lignosulfonate of formula (III) is required. Includes.

[0030] Preferably, the clay is selected from smectite clay minerals such as hydrated aluminum silicate minerals containing montmorillonite, saponite, byderite, nontronite, hectorite, and stebbensite.

[0031] More preferably, the clay is of the formula (Na,Ca) 0.33 (Al 1.67 Mg 0.33 )Si4O 10 (OH)2 . This is a 2-octahedral smectite of nH2O.

[0032] Non-limiting examples of clays suitable for use in the pest-killing composition of the present invention include, for example, smectite clay minerals commercially available under the trade name VOLCLAY® 325.

[0033] Preferably, the heteropolysaccharide is selected from the group consisting of pectin, tamarind seed gum, guar gum, locust bean (carob seed) gum, konjac gum, xanthan gum, alginate, and agar.

[0034] More preferably, the heteropolysaccharide is xanthan gum.

[0035] Preferably, the weight ratio of at least one clay to at least one heteropolysaccharide in the pest-killing composition of the present invention is 8:1 to 15:1, preferably 9:1 to 13:1, more preferably 9:1 to 12:1, and even more preferably 9:1 to 10:1.

[0036] Preferred pest-killing compositions according to the present invention: (a) 40% to 60% by weight of the compound of formula (I), or its phytochemically acceptable salts, stereoisomers, enantiomers, tautomers, or N-oxides, based on the total weight of the composition; (b) 30% to 50% by weight of water based on the total weight of the composition; (c) A surfactant system in an amount of 4% to 10% by weight, based on the total weight of the composition: Based on the total weight of the surfactant system, formula (II) is used for 35% to 40% by weight: HO-(CH2CH2O) x -(CH(CH3)CH2O) y -(CH2CH2O) x’ -H (In the formula, x and x' are either equal to or different from each other, and are integers between 75 and 80. y is an integer between 25 and 30. Here, the polyoxyethylene:polyoxypropylene chain length ratio is 5:1 to 6:1, more preferably 5.1:1 to 5.5:1. At least one polyoxyethylene-polyoxypropylene block copolymer; and Based on the total weight of the surfactant system, 60% to 65% by weight of at least one alkoxylated lignosulfonate of formula (III): [ka] (In the formula, R 1 , R 2 and R 3 These are either equal to or different from each other, and are independently selected from -CH2CH2-, -CH(CH3)CH2-, and -CH2CH2CH2CH2-. i, j, and k are either equal to or different from each other, and are integers from 0 to 15, provided that at least one of i, j, and k is not 0, and X is sodium. Surfactant-based systems containing; (d) at least one type of clay in an amount of 0.08% to 1.2% by weight, based on the total weight of the composition; and (e) 0.06% to 0.15% by weight of at least one heteropolysaccharide based on the total weight of the composition A fluid concentrate for seed treatment containing the following, wherein the weight ratio of at least one clay to at least one heteropolysaccharide in the composition of the present invention is 8:1 to 15:1, preferably 9:1 to 13:1, more preferably 9:1 to 12:1, and even more preferably 9:1 to 10:1.

[0037] A second aspect of the present invention provides a method for controlling insects, mites, nematodes, or mollusks, comprising applying a pest-killing composition according to the present invention to pests, habitats of pests (preferably plants), plants susceptible to attack by pests, or plant reproductive materials (such as seeds). According to this particular aspect of the present invention, methods of treating human or animal bodies by surgery or therapy may be excluded from this method.

[0038] According to a third aspect of the present invention, the use of the pest-killing composition according to the present invention as an insecticide, acaricide, nematicide, or molluscicide is provided. According to this particular aspect of the present invention, methods of treating the human or animal body by surgery or treatment can be excluded from this use.

[0039] When used in the context of parasites in or on the body surface of animals, the term "control" means reducing the number of pests or parasites, eliminating pests or parasites, and / or preventing further infestation by pests or parasites.

[0040] The possibility of one or more chiral carbon atoms in a compound of formula (I) means that the compound can arise in chiral isomers, i.e., enantioisomers or diastereoisomers. Furthermore, atropisomers can arise due to restricted rotations involving single bonds. Formula (I) is intended to encompass all of these possible isomers and mixtures thereof. The present invention encompasses all of these possible isomers and mixtures thereof relating to compounds of formula (I). Similarly, formula (I) is intended to encompass all possible tautomers, if present. The present invention encompasses all possible tautomers relating to compounds of formula (I).

[0041] In each case, the compound of formula (I) exists in a free form, an oxidized form as an N-oxide, a covalent hydrate form, or a salt form, such as an agrochemically usable or agrochemically acceptable salt form. The N-oxide is an oxidized form of a tertiary amine or an oxidized form of a nitrogen-containing aromatic heterocyclic compound. These are described, for example, in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991. The compound of formula (I) according to the present invention also includes hydrates that may be formed during salt formation.

[0042] The compound of formula (I) is commercially available, prepared by known methods, or otherwise obtained using known chemistry.

[0043] Compounds of formula (I) according to the present invention can be prepared, for example, by the methods described in International Publication No. 01 / 00623, International Publication No. 02 / 34734, and U.S. Patent Application Publication No. 2003 / 0232821.

[0044] Salts of the compound of formula (I) can be prepared by known methods. For example, acid addition salts of the compound of formula (I) can be obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with a base can be obtained by treatment with a suitable base or a suitable ion exchange reagent.

[0045] Salts of the compound of formula (I) can be conventionally converted, for example, to acid addition salts of free compound I by treatment with a suitable basic compound or a suitable ion exchange reagent, and to base salts by treatment with a suitable acid or a suitable ion exchange reagent.

[0046] Salts of the compound of formula (I) can be converted to other salts of the compound of formula (I), acid addition salts, such as other acid addition salts, by methods known to themselves, in a suitable solvent in which the inorganic salt forming silver chloride is insoluble and therefore precipitates from the reaction mixture, by treating an inorganic salt, such as a hydrochloride salt, with a suitable metal salt, such as a sodium salt, barium salt, or silver salt of an acid, such as silver acetate.

[0047] Depending on the procedure or reaction conditions, a compound of formula (I) having salt-forming properties can be obtained in free form or as a salt.

[0048] The compounds of formula (I) and, if applicable, their tautomers, may exist in free or salt form, in one form of a possible isomer or as a mixture thereof, depending on the number, absolute and relative configuration of chiral carbon atoms present in the molecule and / or the configuration of non-aromatic double bonds present in the molecule, in the form of pure isomers such as anticarpone and / or diastereomers, or as isomer mixtures such as enantiomer mixtures, such as racemates, diastereomer mixtures or racemic mixtures; the present invention relates to pure isomers and also to all possible isomer mixtures, and should be understood in this sense above and below, respectively, even if stereochemical details are not specifically described for each.

[0049] A stereoisomerized or racemic mixture of the compound of formula (I) can be separated into pure diastereomers or racemates based on physicochemical differences of the components, for example by fractional crystallization, distillation and / or chromatography, in the free or salt form obtained depending on the selected starting materials and procedure.

[0050] Enantiomer mixtures such as racemates obtained by similar methods can be broken down into optical enantiomers by known methods, for example, by recrystallization from an optically active solvent, by chromatography in a chiral adsorbent, for example by high-performance liquid chromatography (HPLC) in acetylcellulose using a suitable microorganism, by cleavage by a specific immobilized enzyme via the formation of an inclusion compound, for example using a chiral crown ether into which only one enantiomer is combined, or by conversion to a diastereomer salt, for example by reacting the basic final product racemate with an optically active acid such as a carboxylic acid, for example camphoric acid, tartaric acid, or malic acid, or a sulfonic acid, for example camphor sulfonic acid, and separating the diastereomer mixture thus obtained, for example by fractional crystallization based on different solubility, to obtain a diastereomer from which the desired enantiomer can be released by the action of a suitable substance, for example a basic substance.

[0051] Pure diastereomers or enantiomers can be obtained not only by separating a suitable mixture of isomers according to the present invention, but also by generally known diastereoselective or enantioselective synthesis methods, such as using starting materials with stereochemical properties, and performing the method according to the present invention.

[0052] When individual components have different biological activities, it is advantageous to isolate or synthesize biologically more effective isomers, such as enantiomers or diastereomers, or mixtures of isomers, such as mixtures of enantiomers or diastereomers.

[0053] The compounds of formula (I) and optionally their tautomers may also be obtained in free form or salt form, optionally in hydrate form, and / or in other solvents, such as solvents that have been used to crystallize compounds existing in solid form.

[0054] The ethylene oxide and propylene oxide block copolymer of formula (II) is commercially available, prepared by known methods, or otherwise obtained using known chemistry.

[0055] Alkoxylated lignosulfonates of formula (III) are commercially available, prepared by known methods, or otherwise obtained using known chemistry. For example, alkoxylated lignosulfonates can be obtained by alkoxylation of lignosulfonates using known alkylene oxide reagents such as ethylene oxide. Particularly desirable alkoxylated lignosulfonates of formula (III) are selected from the group consisting of ethoxylated lignosulfonates, propoxylated lignosulfonates, and butoxylated lignosulfonates. Other useful alkoxylated lignosulfonates of formula (III) are compounds obtained, for example, from mixed alkoxylations in which the alkylene oxide units introduced between ethylene oxide and propylene oxide are different or alternate.

[0056] Lignosulfonates that can be used to prepare the alkoxylated lignosulfonates of formula (III) are commercially available, prepared by known methods, or otherwise obtained using known chemistry.

[0057] The lignosulfonates used in the formation of the alkoxylated lignosulfonates of formula (III) are well known in the art and can be derived, for example, from the sulfite pulping of wood and from the sulfonation of lignin derived from wood kraft pulping. The kraft lignin material used is typically in salt form (i.e., sodium, potassium, etc.). Typically, lignosulfonates can be obtained by sulfonation of sulfite pulp wastewater from wood conversion. It is preferable to use purified lignosulfonate material from which carbohydrates and other polysaccharide components have been partially or completely removed.

[0058] "Kraft lignin" typically refers to material recovered from alkaline pulp black liquor, such as that obtained through krafting, caustic soda, and other well-known alkaline pulping processes.

[0059] Typically, alkoxylated lignosulfonates of formula (III) have a specific degree of sulfonation. The degree of sulfonation is a function of the amount of organically bound sulfur present in the material and can be determined by any suitable method known to those skilled in the art. For example, sulfonation can be determined by subtracting the sum of the amount of sulfur present in the starting material and the sulfur present in free sulfites and sulfates from the total sulfur content. The amount of free sulfites, the amount of free sulfates, and the total amount of sulfur can be determined by any method known to those skilled in the art.

[0060] Compound (I) is an active ingredient with a highly favorable biocidal range and good resistance in warm-blooded species, fish, and plants, and is of prophylactic and / or therapeutic value in the field of pest control even at low application doses. Compound (I) may have a beneficial safety profile for non-target species such as wasps, and therefore may have a good toxicity profile. Compound (I) may act on all or individual developmental stages of pests such as insects or representative mites (Acarina) that are usually susceptible but also resistant. The insecticidal or acaricidal activity of compound (I) can be expressed directly, i.e., immediately, or only after a certain period of time, such as during molting, by killing pests, or indirectly, for example, by reducing oviposition and / or hatching rates.

[0061] Examples of the above-mentioned pests are as follows: From the order Acarina, for example, Acaritus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp.) Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus (spp.), genera Rhizoglyphus, Sarcoptes, Steneotarsonemus, Tarsonemus, and Tetranychus; From the order Anoplura, for example, The genera Haematopinus, Linognathus, Pediculus, Pemphigus, and Phylloxera; From the order Coleoptera, for example, Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Atenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Connoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa ​​decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maledra castanea, Megascelis spp.) Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp.), Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabaeidae family, Sitophilus spp., Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp., and Trogoderma spp.; From the order Diptera, for example, Genus Aedes, Anopheles, Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia, Calliphora erythrocephala, Ceratitis, Chrysomyia, Culex, Cuterebra, Dacus, Delia, Drosophila melanogaster, Fannia spp.), Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia (spp.), Rhagoletis spp., Riveria quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp., and Tipula spp.; From the order Hemiptera, for example, Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp.) Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.), *Thyanta* spp., *Triatoma* spp., *Vatiga illudens*; Acyrthosium pisum, Adalges spp., Agalliana ensigera, Aganoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella (spp.), Aphididae family, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp.), Chrysomphalus aonidium, Greenhouse scale insect (Chrysomphalus dictyospermi), Cicadella spp., White leafhopper (Cofana spectra), Cryptomyzus spp., Cicadulina spp., Flat scale insect (Coccus hesperidum), Dalbulus maidis, Dialeurodes spp., Citrus psyllid (Diaphorina citri), Diuraphis noxia, Dysaphis spp., Empoasca spp., Apple woolly aphid (Eriosoma larigerum), Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi), Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.), Neotoxoptera sp., Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp., Phorodon humuli), Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Cotton flea beetle (Pseudatomoscelis seriatus), Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Lightning leafhopper (Recilia dorsalis), Rhopalosiphum spp., Saissetia spp., Scaphoideus (spp.), Schizaphis spp., Sitobion spp.), Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris; From the order Hymenoptera, for example, The genera Acromyrmex, Arge, Atta, Cephus, Diprion, Diprionidae, Gilpinia polytoma, Hoplocampa, Lasius, Monomorium pharaonis, Neodiprion, Pogonomyrmex, Slenopsis invicta, Solenopsis, and Vespa; From the order Isoptera, for example, Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminate From the order Lepidoptera, for example, Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis), Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp.), Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp.), Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta), Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.), pine moth (Panolis flammea), Papaipema nebris, cotton beetle (Pectinophora gossypiela), coffee leafminer (Perileucoptera coffeella), Pseudaletia unipuncta, potato moth (Phthorimaea operculella), cabbage white butterfly (Pieris rapae), Pieris spp., diamondback moth (Plutella xylostella), Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia (spp.), genera Sparganothis, Spodoptera, Sylepta derogate, Synanthedon, Thaumetopoea, Tortrix, Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.); From the order Mallophaga, for example, The genera Damalinea and Trichodectes; From the order Orthoptera, for example, The genera Blatta, Blattella, Grillosa, Leucophaea maderae, Locusta, Neocurtilla hexadactyla, Periplaneta, Scapteriscus, and Schistocerca; From the order Psocoptera, for example, Liposcelis genus (Liposcelis spp.) From the order Siphonaptera, for example, The genera Ceratophyllus, Ctenocephalides, and Xenopsylla cheopis; From the order Thysanoptera, for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinotothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp. From the silvery-eyed species (Thysanura), for example, the European silverfish (Lepisma saccharina).

[0062] The pest-killing compositions according to the present invention can be used to control, i.e., suppress or destroy, the above-mentioned types of pests that occur particularly in plants, especially useful plants and ornamental plants in agriculture, horticulture and forestry, or in organs such as fruits, flowers, leaves, stems, tubers or roots of such plants, and in some cases even plant organs that are formed at a later time remain protected from these pests.

[0063] According to the present invention, “useful plants” typically include the following perennial or annual plants: Cereals such as barley, corn, millet, oats, rice, rye, sorghum, tritordeum, and wheat, amaranth, buckwheat, chia, quinoa, and canuar; Fruits and tree nuts such as grapes (table grapes and wine grapes), almonds, apples, apricots, avocados, bananas, wild strawberries, blueberries, breadfruit, cocoa, cashews, cherimoya, cherries, chestnuts (nuts), Amelanchier, citrus fruits (including grapefruit, lime, lemon, orange, and calamansi), coconuts, coffee, cranberries, currants, dates, feijoa fruit, figs, hazelnuts, gooseberries, guavas, kiwis, lychees, macadamia nuts, mangoes, nectarines, olives, papayas, passion fruit, peaches, pears, pecans, persimmons, pineapples, pistachios, plums (including prunes), pomegranates, quince, raspberries, strawberries, Suriname cherries, and walnuts; Korean thistle, asparagus, green beans (snap beans, string beans, dried beans, edible beans), beets (see top), broccoli / Italian turnip, Brussels sprouts, cabbage (including Chinese cabbage), carrots, cauliflower, celeriac, celery, chickpeas, chives, Savoy cabbage (including kale), cucumbers, edamame, eggplant, endive, peas (garden Vegetables such as peas, dried peas, edible peas, garlic, horseradish, turnips and cabbage, leeks, lentils, lettuce, melons, cultivated mushrooms, mustard and other leafy greens, okra, onions, parsley, angelica tree, pepper, shishito peppers, potatoes, prickly pear fruit, pumpkins, radishes, rhubarb, rutabaga, burdock, spinach, squash (summer and winter varieties), sweet corn, sweet potatoes, Swiss chard, taro, tomatoes / ground cherries, turnips and watermelons; Agricultural products such as sugar beets, sugarcane, tobacco, peanuts, and soybeans; Oilseed crops such as rapeseed (canola), mustard, camelina, seaweed, sunflower, poppy, sesame, and safflower; For example, fodder crops such as alfalfa, clover, cowpea, vetch, burdock, lupine, feed beet, poison ryegrass, Kentucky bluegrass, bovine, and orchardgrass; Fiber crops such as cotton, flax, hemp, jute, and sisal; Forest plants including coniferous species such as larch, fir or pine, and temperate and tropical hardwoods (e.g., oak, birch, beech, teak or mahogany), as well as arid species such as eucalyptus; Hops, maple (maple syrup), tea, natural rubber plants and turfgrasses (horticultural crops such as bentgrass, Kentucky bluegrass, poison ryegrass, oxtail grass, Bermuda grass, centipede grass, crested hairgrass, Pennisetum alopecuroides, St. Augustine grass, Zoysia japonica, moss, timothy grass, and broad-leaved Miscanthus grass); Examples include begonia, dahlia, geranium, impatiens, petunia, coleus, marigold, pansy, snapdragon, African violet, azalea, chrysanthemum, flower bulbs, hydrangea, lily, orchid, poinsettia, rose, astilbe, coreopsis, delphinium, carnation, heuchera, hosta, phlox, rudbeckia, salvia, vinca, columbine, large-leaved hosta, chrysanthemum (garden Floriculture, greenhouse and nursery plants including flowers, broad-leaved or evergreen trees such as chrysanthemum, ivy, ornamental grass, peony, delphinium, gladiolus, iris, snapdragon, tulip, eucalyptus, pittosporum, ferns, anthurium, dieffenbachia, dracaena, ficus, philodendron, spathiphyllum, bromeliad, cactus, palm, balsam fir, picea, American pine, Fraser fir, noble fir, Scots pine, white pine, magnolia, ash, elm, ornamental cherry, ornamental plum, hawthorn, redbud, and rowan; Propagation materials such as bare-root seedlings, cuttings, liners, cell-grown seedlings, seeds, tissue-cultured small plants, and prefinished plants; For example, allspice, Angelica species (Angelica spp.), anise, annatto, yellow radish, jasmine, basil (all species), bay laurel (cultivated varieties), bladderwrack (seaweed), Bolivian coriander, borage, calendula (used as a herb), candlenut, caper, caraway, cardamom, cassia spice, cinnamon, clary sage, clove, catnip, chamomile, chervil, chicory, sice, cilantro, comfrey, coriander, mustard greens, cumin, curry, dill, fennel, fenugreek, Culinary herbs and spices such as fillet (cultivated), finger root, galangal, ginger, hops, bitter mint, hyssop, lavender, lemon oil, lemon thyme, lavage, mace, mahalyb, marabatrum, marjoram, mint (all varieties), mugwort, nutmeg, oregano, orris root, paprika, parsley, pepper, rosemary, rue, saffron, sage (all varieties), savory (all varieties), wood sorrel, tarragon, thyme, turmeric, vanilla, wasabi and watercress; and For example, medicinal herbs such as alum, Artemisia spp., astragalus, bordeaux, comfrey, coneflower, fenugreek, feverfew, foxglove, ginkgo, ginseng, goat's rue, hydrastis, gypsy wort, bitter mint, horsetail, lavender, licorice, red almond, mullein, nettle, passionflower, patchouli, mint, pokeweed, scutellaria, wood sorrel, St. John's wort, senna, sow thistle, stevia, chrysanthemum, witch hazel, cuckoo flower, bitter wormwood, yarrow, yerba buena, and ylang-ylang tree.

[0064] This list is not intended to be limiting in any way, but preferably, useful plants may be selected from the group consisting of cereals (e.g., barley, corn, rice, rye, sorghum, oats, wheat), vegetables (e.g., green beans, cucumbers, eggplants, lettuce, melons, pumpkins, spinach, shishito peppers, watermelons), crops (e.g., sugar beets, peanuts), oilseed crops (e.g., sunflowers, canola), fodder crops (e.g., alfalfa), and fiber crops (e.g., cotton).

[0065] The pest-killing compositions according to the present invention are particularly suitable for controlling pests, including soil-dwelling, early-stage leaf-eating, and sap-sucking insects, such as root-cutting insects, aphids, thrips, Coleoptera species that feed on leaves and stems, such as species of the genus Atomaria and flea beetles, and several species of Lepidoptera species such as species of the genus Alabama, against cereals (e.g., barley, corn, rice, rye, sorghum, oats, wheat), vegetables (e.g., green beans, cucumbers, eggplants, lettuce, melons, pumpkins, spinach, shishito peppers, watermelons), crops (e.g., sugar beets, peanuts), oilseed crops (e.g., sunflowers, canola), fodder crops (e.g., alfalfa), and fiber crops (e.g., cotton).

[0066] The active ingredient according to the present invention is particularly suitable for controlling armyworms (Mamestra) (preferably in vegetables), codling moths (Cydia pomonella) (preferably in apples), species of the genus Empoasca (preferably in vegetables and vineyards), species of the genus Leptinotarsa ​​(preferably in potatoes), and rice stem borer (Chilo supressalis) (preferably in rice).

[0067] In a further embodiment, the present invention also relates to plant parasitic nematodes (endoparasitic, semi-endoparasitic, and ectoparasitic nematodes), particularly root-knot nematodes, northern root-knot nematodes (Meloidogyne hapla), sweet potato root-knot nematodes (Meloidogyne incognita), Javan root-knot nematodes (Meloidogyne javanica), arenaria root-knot nematodes (Meloidogyne arenaria), and other species of the genus Meloidogyne; cyst-forming nematodes, potato cyst nematodes (Globodera rostochiensis), and other species of the genus Globodera; wheat cyst nematodes (Heterodera avenae), soybean cyst nematodes (Heterodera glycines), sugar beet cyst nematodes (Heterodera schachtii), clover cyst nematodes (Heterodera (trifolii), and other species of the cyst nematode genus Heterodera; Seed gall nematodes, species of the genus Anguina; Stem nematodes and leaf nematodes, species of the genus Aphelenchoides; Sting nematodes, Belonolaimus longicaudatus, and other species of the genus Belonolaimus; Pine wood nematode, Bursaphelenchus xylophilus) and other species of the genus Bursaphelenchus; petroleum nematodes, species of Criconema, Criconemella, Criconemoides, and Mesocriconema; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other species of the genus Ditylenchus; cycad nematodes and species of Dolichodorus;Spiral nematodes, Heliocotylenchus multicinctus and other species of the genus Helicotylenchus; Sheath and sheathoid nematodes, species of the genera Hemicycliophora and Hemicriconemoides; species of the genus Hirshmanniella; Spear nematodes, species of the genus Hoploaimus; False root-knot nematodes, species of the genus Nacobbus; Pufferfish nematodes, Longidorus elongatus Longidorus species (elongatus) and other species of the genus Longidorus; pin nematodes, species of the genus Pratylenchus; root nematodes, wheat root nematodes (Pratylenchus neglectus), northern root nematodes (Pratylenchus penetrans), Platylenchus curvitatus, Platylenchus goodeyi and other species of the genus Pratylenchus; banana root nematodes (Radopholus similis) and other species of the genus Radopholus; false sedge nematodes, Rotylenchus robustus, Rotylenchus reniformis Rotylenchus species (reniformis) and other Rotylenchus species; species of the genus Scutellonema; Trichodorus primitivus and other Trichodorus species; species of the genus Paratrichodorus;Plant parasitic nematodes such as Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other species of the genus Tylenchorhynchus; Tylenchulus species and other species of the genus Tylenchulus; Xiphenema species and other species of the genus Xiphenema; and species of the genera Subanguina, Hypsoperine, Macroposthonia, Melinius, Punctodera and Quinisulcius This may relate to methods for preventing damage to plants and parts thereof caused by other plant-parasitic nematode species (such as spp.).

[0068] The pest-killing compositions of the present invention may also be active against mollusks. Examples include, for example, the families Ampullariidae; the genus Arion (Arion ater, Arion circumscriptus, Arion hortensis, Arion rufus); the family Bradybaenidae (Bradybaena fruticum); the genus Cepaea (Cepaea hortensis, Cepaea hortensis) Nemoralis); ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Heliceria (H. itala, H. obvia); Helicidae (Helicigona albumum) arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Monoa Examples include the genera Lymnaea, Milax (M. gagates, M. marginatus, M. sowerbyi), Opeas, Pomacea (Pomacea canaticulata), Vallonia, and Zanitoides.Compounds according to formula (I) may prove useful in controlling populations of insects that have developed resistance to neonicotinoid class pesticides ("neonicotinoids") that were previously susceptible to them. Such neonicotinoid-resistant insects may include insects of the order Lepidoptera, or Hemiptera, particularly insects of the family Aphididae.

[0069] Neonicotinoids represent a well-known class of insecticides introduced to the market following the practical application of pyrethroids (Nauen & Denholm, 2005: Archives of Insect Biochemistry and Physiology 58:200-215). These are highly valuable insect control agents because they show little to no cross-resistance to older classes of insecticides, where resistance problems are significant. However, reports of insect resistance to neonicotinoid insecticides are increasing. Therefore, this increasing resistance of insects to neonicotinoid insecticides poses a significant threat to the cultivation of many commercially important crops, fruits, and vegetables, and thus there is a need to find alternative insecticides that can control neonicotinoid-resistant insects (i.e., insecticides that do not show any cross-resistance to the neonicotinoid class).

[0070] Resistance can be defined as "a genetic change in the susceptibility of a pest population, which is reflected in the repeated failure to achieve the expected control effect when a product containing an insecticidal active ingredient is used in accordance with the label recommendations for the pest species" (IRAC). Cross-resistance occurs when resistance to one insecticide leads to resistance to another insecticide via the same biochemical mechanism. This can occur within or between the chemical classes of insecticides. Cross-resistance can occur even if the resistant insect has never been exposed to one of the chemical classes of insecticides.

[0071] Two of the main mechanisms related to neoniocotinoid resistance include the following: (i) Target site resistance relating to the substitution of one or more amino acids in the insecticide target protein (i.e., nicotinic acetylcholine receptor); and (ii) Metabolic tolerance, such as the high oxidative detoxification effect of neonicotinoids due to the overexpression of monooxygenase.

[0072] For a general overview of insect resistance to neoniocotinoid insecticides, see, for example, Pesticide Biochemistry and Physiology (2015), 121, 78-87, or Advances in Experimental Medicine and Biology (2010), 683 (Insect Nicotinic Acetylcholine Receptors), 75-83. Cytochrome P450 monooxygenases are important metabolic pathways involved in the detoxification / activation of xenobiotics. Therefore, P450 monooxygenases play a crucial role in insecticide resistance.

[0073] Due to the presence of numerous P450s (60-111) in various species, and the broad substrate specificity of some P450s, P450 monooxygenases possess a specialized array of such metabolizable substrates. Studies of monooxygenase-mediated resistance have shown that resistance may be due to increased expression (via increased transcription) of a P450 involved in the detoxification of insecticides, or it may be due to changes in the structural gene itself. Therefore, metabolic cross-resistance mechanisms affect not only insecticides from a certain class (e.g., neonicotinoids) but also seemingly unrelated insecticides. For example, cross-resistance between neonicotinoids and pymetrozine in the tobacco whitefly (Bemisia tabaci) has been reported by Gorman et al (Pest Management Science 2010, pp. 1186-1190). Alternatively, for example, regarding evidence related to detoxification via P450, see, for example, Harrop, Thomas WR and al. Pest Management Science (2018), 74(7), pp. 1616-1622, and the cited literature.

[0074] Nicotinoid target site tolerance has been well studied, and it has been shown that modified active sites of nicotinic acetylcholine receptors can lead to nicotinoid tolerance. See, for example, Bass et al. BMC Neuroscience (2011), 12, p 51, and Pest Management Science (2018), 74(6), 1297-1301.

[0075] The term “crop” should be understood to also include crops transformed by the use of recombinant DNA technology, for example, to synthesize one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria, particularly bacteria of the genus Bacillus.

[0076] Toxins that may be expressed by such transgenic plants include, for example, insecticidal proteins derived from Bacillus cereus or Bacillus popilliae; or δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, insecticidal proteins derived from Bacillus thuringiensis or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A; or bacterial colony-forming nematodes, such as Photorhabdus luminescens, Xenorhabdus nematophilus, and other species of the genus Photorhabdus (Photorhabdus spp. or Xenorhabdus). Insecticidal proteins (spp.); toxins produced by animals, such as scorpion venom, arachnid venom, wasp venom, and neurotoxins specific to other insects; toxins produced by fungi, such as Streptomycetes toxins; plant lectins, such as pea lectin, barley lectin, or saxifrage lectin; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patain, cystatin, and papain inhibitors; lysine, maize-RIP, abrin, rufin, saporine Examples include ribosome-inactivating proteins (RIPs) such as ribosomal protein (RIP) or briodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, and HMG-COA-reductase; ion channel blockers such as sodium channel or calcium channel blockers; juvenile hormone esterase, diuretic hormone receptor, stilbenzyl synthase, bibenzyl synthase, chitinase, and glucanase.

[0077] In relation to the present invention, δ-endotoxins are understood, for example, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A, and more specifically, as hybrid toxins, cleavage toxins and modified toxins. Hybrid toxins are produced by recombination through novel combinations of different domains of those proteins (see, for example, International Publication No. 02 / 15701). Cleavage toxins, such as cleavage Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the natural toxin are substituted. In such amino acid substitutions, preferably, a protease recognition sequence that does not exist in nature is inserted into the toxin; for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see International Publication No. 03 / 018810).

[0078] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in European Patent Publication No. 0374753, International Publication No. 93 / 07278, International Publication No. 95 / 34656, European Patent Publication No. 0427529, European Patent Publication No. 451878, and International Publication No. 03 / 052073.

[0079] Methods for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparations are known, for example, from International Publication No. 95 / 34656, European Patent Application Publication No. 0367474, European Patent Application Publication No. 0401979, and International Publication No. 90 / 13651.

[0080] The toxins contained in transgenic plants confer resistance to pests. Such insects are found in various insect taxonomic groups, but are particularly common in beetles (Coleoptera), diptera (Diptera), and moths (Lepidoptera).

[0081] Transgenic plants containing one or more genes encoding insecticidal resistance and expressing one or more toxins are known, and some of them are commercially available. Examples of such plants include: YieldGard® (maize variety expressing Cry1Ab toxin); YieldGard Rootworm® (maize variety expressing Cry3Bb1 toxin); YieldGard Plus® (maize variety expressing Cry1Ab and Cry3Bb1 toxins); Starlink® (maize variety expressing Cry9C toxin); Herculex I® (maize variety expressing Cry1Fa2 toxin and the enzyme phosphinothrysin N-acetyltransferase (PAT) for resistance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety expressing Cry1Ac toxin); Bollgard I® (cotton variety expressing Cry1Ac toxin); Bollgard These include II (registered trademark) (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot (registered trademark) (a cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf (registered trademark) (a potato variety expressing Cry3A toxin); NatureGard (registered trademark), Agrisure (registered trademark) GT Advantage (GA21 glyphosate resistance trait), Agrisure (registered trademark) CB Advantage (Bt11 corn borer (CB) trait), and Protecta (registered trademark).

[0082] Further examples of such transgenic crops are as follows: 1. Bt11 maize, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France), registration number C / FR / 96 / 05 / 10. Genetically modified maize that has been given resistance to attacks by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the cleavage Cry1Ab toxin. Bt11 maize also expresses the enzyme PAT through genetic modification to obtain resistance to the herbicide glufosinate ammonium.

[0083] 2. Bt176 maize, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France), registration number C / FR / 96 / 05 / 10. Genetically modified maize that has been given resistance to attacks by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the Cry1Ab toxin. Bt176 maize also expresses the enzyme PAT through genetic modification to obtain resistance to the herbicide glufosinate ammonium.

[0084] 3. MIR604 maize, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France), registration number C / FR / 96 / 05 / 10. This maize was made insect-resistant through transgenic expression of a modified Cry3A toxin. The toxin is Cry3A055, modified by the insertion of a cathepsin-G protease recognition sequence. The preparation of such transgenic maize plants is described in international publication 03 / 018810.

[0085] 4. MON 863 maize, registration number C / DE / 02 / 9, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium). MON 863 expresses the Cry3Bb1 toxin and is resistant to certain Coleoptera insects.

[0086] 5. IPC 531 cotton manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium), registration number C / ES / 96 / 02.

[0087] 6. 1507 maize, registration number C / NL / 00 / 10, manufactured by Pioneer Overseas Corporation (Avenue Tedesco, 7 B-1160 Brussels, Belgium). Genetically modified maize for the expression of protein Cry1F to obtain resistance to certain Lepidoptera insects and PAT protein to obtain resistance to the herbicide glufosinate ammonium.

[0088] 7. NK603×MON 810 maize, registration number C / GB / 02 / M3 / 03, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium). This hybrid maize variety is bred using conventional methods by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize also expresses, through genetic modification, the protein CP4 EPSPS obtained from the Agrobacterium sp. strain CP4, which provides resistance to the herbicide Roundup® (containing glyphosate), and the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki, which provides resistance to certain Lepidoptera, including the European corn borer.

[0089] Transgenic crops of insect-tolerant plants are also described in the BATS (Zentrum fuer Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003 (http: / / bats.ch).

[0090] The term “crops” should be understood to include crops transformed by the use of recombinant DNA technology so that selectively active antipathogenic substances can be synthesized, such as so-called “pathogenicity-associated proteins” (PRP, see, for example, European Patent Application Publication No. 0392225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from European Patent Application Publication No. 0392225, International Publication No. 95 / 33818 and European Patent Application Publication No. 0353191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.

[0091] Crops can also be improved to increase their resistance to fungal pathogens (e.g., Fusarium, anthracnose, or Phytophthora), bacteria (e.g., Pseudomonas), or viruses (e.g., potato leaf curl virus, tomato yellow necrosis virus, cucumber mosaic virus).

[0092] The crops include varieties that have high resistance to nematodes, such as soybean cyst nematodes.

[0093] Crops that are abiotically tolerant include, for example, those that exhibit high tolerance to drought, high salinity, high temperature, low temperature, frost, or light due to the expression of NF-YB or other proteins known in the art.

[0094] Examples of antipathogenic substances that may be expressed by such transgenic plants include ion channel blockers such as sodium channel or calcium channel blockers, such as viral KP1, KP4, or KP6 toxins; stilbene synthase; vibenzyl synthase; chitinase; glucanase; so-called "pathogenicity-associated proteins" (PRPs; see, for example, European Patent Application Publication No. 0392225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics (see, for example, International Publication No. 95 / 33818); or proteins or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes" as described in International Publication No. 03 / 000906).

[0095] Further applications of the compositions according to the present invention include the protection of stored goods and storage environments, and the protection of raw materials (such as wood and textiles), flooring materials and buildings, and hygiene, particularly the protection of humans, livestock and productive livestock from the above-mentioned types of pests.

[0096] The present invention also provides a method for controlling pests (such as mosquitoes and other pathogenic animals; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, the method for controlling pests comprises the step of applying the composition of the present invention to a target pest, its habitat, or surface or substrate by brush application, roller application, spraying, coating, or immersion. For example, IRS (Indoor Residual Spray) application to surfaces such as walls, ceilings, or floors is envisioned by the method of the present invention. In another embodiment, it is envisioned that such a composition be applied to a substrate such as a nonwoven or fabric material in the form of a net, clothing, bedding, curtains, and tents (or in a form that can be used to manufacture these). A further object of the present invention is a substrate selected from nonwoven and fabric materials comprising a composition containing a compound of formula (I).

[0097] In one embodiment, a method for controlling such pests includes the step of applying an biocidally effective amount of the pesticide composition of the present invention to a target pest, its habitat, or a surface or substrate, so as to impart effective persistent pest control activity to the surface or substrate. Such application may be carried out by brush application, roller application, spraying, coating, or immersion of the composition of the present invention. For example, IRS application on surfaces such as walls, ceilings, or floors is envisioned by the method of the present invention to impart effective persistent pest control activity to the surface. In another embodiment, such a composition is envisioned for persistent control of pests on substrates such as fabric materials in the form of nets, clothing, bedding, curtains, and tents (or forms that may be used in the manufacture thereof).

[0098] When used in the context of parasites in the body or surface of animals, the term “effective dose” refers to the amount or dosage of the compound or salt thereof of the present invention that, in one or more doses, produces the desired effect in the body or surface of the animal. The effective dose can be readily determined by a diagnostician skilled in the art by using known techniques and by observing the results obtained under similar circumstances. In determining the effective dose, the diagnostician will consider, but will not be limited to, the following factors: the species of mammal; its size, age, and general health; the parasite being controlled and the degree of invasiveness; the specific disease or disorder associated; the degree of complications or severity in the disease or disorder; the individual's response; the specific compound administered; the mode of administration; the bioavailability characteristics of the administered preparation; the selected dosage administration plan; the use of concomitant drugs; and numerous other relevant circumstances.

[0099] The substrate, including the nonwoven fabric, cloth, or net to be treated, may be made from natural fibers such as cotton, raffia, jute, flax, sisal, linen, or wool, or from synthetic fibers such as polyamide, polyester, polypropylene, or polyacrylonitrile. Polyester is particularly preferred. Methods for treating textiles are known, for example, from International Publication No. 2008 / 151984, International Publication No. 03 / 034823, U.S. Patent No. 5631072, International Publication No. 2005 / 64072, International Publication No. 2006 / 128870, European Patent No. 1724392, International Publication No. 2005113886, or International Publication No. 2007 / 090739.

[0100] A further field of application of the composition according to the present invention is the field of trunk injection / trunk treatment of all ornamental trees and all kinds of fruit trees and nut-bearing trees.

[0101] In the field of tree trunk injection / trunk treatment, the compounds according to the present invention are particularly suitable for the above-mentioned wood-boring insects of the orders Lepidoptera and Coleoptera, and especially for the wood-borers listed in the table below.

[0102] [Table 1]

[0103] [Table 2] TIFF0007873249000008.tif251165 TIFF0007873249000009.tif242165

[0104] The pest-killing compositions of the present invention can be used to control any insect pests that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, pillbugs, mites, mole crickets, scale insects, mealybugs, ticks, spittlebugs, southern chinch bugs, and ground bugs. The present invention can also be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0105] In particular, the pest-killing compositions of the present invention are effective against ground insects (genus Cyclocephala (e.g., masked chafer, C. lurida), Rhizotrogus (e.g., European chafer, R. majalis), Cotinus (e.g., blue-spotted chafer, C. nitida), Popillia (e.g., Japanese beetle, P. japonica), Phyllophaga (e.g., May / June beetle), and Ataenius). (e.g., Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g., red velvet beetle, M. castanea, and Tomarus spp.), cottony cushion scales (Margarodes spp.), mole crickets (tawny, southern, and brachyptera; Scapteriscus spp., mole cricket (Gryllotalpa africana)), and leather jackets (European crane fly, Tipula genus). It can be used to control insect pests that feed on turfgrass roots, including spp.)).

[0106] The pest-killing composition of the present invention can also be used to control insect pests of turfgrass that live in straw, including armyworms (such as Spodoptera frugiperda and common armyworms (such as Pseudaletia unipuncta)), cutworms, weevils (such as Sphenophorus spp., S. venatus verstitus and S. parvulus) and sod webworms (such as Crambus spp., tropical sod webworm, and Herpetogramma phaeopteralis).

[0107] The pest-killing composition of the present invention can also be used to control insect pests that inhabit the ground and feed on grass leaves, including the Southern kink bug (Blissus insularis, etc.), Bermudagrass mites (Eriophyes cynodoniensis), African rhodesgrass mealybugs (Antonina graminis), two-lined spittlebugs (Propsapia bicincta), leafhoppers, cutworms (Noctuidae), and wheat aphids.

[0108] The pest-killing composition of the present invention can also be used to control other turfgrass pests, such as the red imported fire ant (Solenopsis invicta), which builds ant mounds in lawns.

[0109] In the field of hygiene, the compositions according to the present invention are effective against external parasites such as hard ticks, soft ticks, scabies mites, chiggers, flies (stable flies and licking flies), parasitic fly larvae, lice, pubic lice, biting lice, and fleas.

[0110] Examples of such parasites are as follows: Among the orders Anoplurida, these include the genera Haematopinus, Linognathus, Pediculus, Phtirus, and Solenopotes. Among the orders Mallophagida, the genera Trimenopon, Menopon, Trinoton, Bovicola, Werneckiella, Lepikentron, Damalina, Trichodectes, and Felicola are included. Among the order Diptera and its suborders Nematocerina and Brachycerina, for example, the genera Aedes, Anopheles, Culex, Simulium, Eusimulium, Phlebotomus, Lutzomyia, Culicoides, Chrysops, Hybomitra, Atylotus, Tabanus, and Haematopota spp.) , Philippomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp. (spp.), Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., and Melophagus spp.. Within the order Siphonapterida, for example, there are genera such as Pulex spp., Ctenocephalides spp., Xenopsylla spp., and Ceratophyllus spp.. Among the order Heteropterida, for example, there are genera such as bed bugs (Cimex spp.), assassin bugs (Triatoma spp.), Rhodnius spp., and Panstrongylus spp. Among the order Blattardia, for example, the oriental cockroach (Blatta orientalis), the American cockroach (Periplaneta americana), the German cockroach (Blattelagermanica), and the genus Supella. Among the subclass Acaria (Acarida), suborder Metastigmata, and suborder Mesostigmata, for example, the genera Argas, Ornithodorus, Otobius, Ixodes, Amblyomma, Boophilus, Dermacentor, Haemophysalis, Hyalomma, Rhipicephalus, Dermanyssus, and Railietia. (spp.), Pneumonyssus spp., Sternostoma spp., and Varroa spp.. Among the orders Acari (Actinedida) (Prostigmata) and Acaridida (Astigmata), for example, the genera Acarapis, Cheyletiella, Ornithocheyletia, Myobia, Psorergates, Demodex, Trombicula, Listrophorus, Acarus, Tyrophagus, Caloglyphus, and Hypodectes. spp.), Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp..

[0111] The pest-killing composition of the present invention is also suitable for protecting materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cardboard, leather, flooring materials, and buildings from insect infestation.

[0112] The pest-killing composition of the present invention can be used, for example, against the following pests: European house beetle (Hylotrupes bajulus), Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, pine wood beetle (Ernobius mollis), large wood beetle (Priobium carpini), flat bark beetle (Lyctus brunneus), African flat bark beetle (Lyctus africanus), American flat bark beetle (Lyctus planicollis), oak flat bark beetle (Lyctus *) and beetles such as Dinoderus minutus, as well as hymenopteran insects such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus Termites such as *Lucifugus*, *Mastotermes darwiniensis*, *Zootermopsis nevadensis*, and *Coptotermes formosanus*, as well as silverfish such as *Lepisma saccharina*.

[0113] The compound of formula (I) can be used as a pesticide in its unmodified form, but it is generally incorporated into compositions using various methods with carriers, solvents, and additives such as surfactants.

[0114] The pest-killing compositions of the present invention can be in various physical forms, such as powder, gel, wettable powder, water-dispersible granules, water-dispersible tablets, effervescent pellets, suspension concentrates, seed treatment fluid concentrates, emulsifying concentrates, microemulsifying concentrates, oil-in-water emulsions, oily flowables, aqueous dispersions, oily dispersions, sasporumulons, capsule suspensions, emulsifying granules, soluble liquids, water-soluble concentrates (containing water or a hydrated organic solvent as a carrier), impregnated polymer films, or other forms known from, for example, the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such compositions can be used directly or diluted before use. Dilution can be performed, for example, with water, liquid fertilizers, trace elements, biological substances, oils, or solvents.

[0115] Preferably, the pest-killing composition of the present invention is a fluid concentrate for seed treatment.

[0116] The term "seed treatment fluid concentrate" is intended to refer to a formulation in which one or more solid active ingredients are dispersed in water, usually at high concentrations.

[0117] A finely ground compound is completely mixed with an auxiliary agent to obtain a fluid concentrate for seed treatment, from which a suspension of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants and plant propagation materials can be treated and protected from microbial ectoparasitism by spraying, pouring, or immersion.

[0118] To obtain compositions in the form of fine solids, granules, solutions, dispersions, or emulsions, the compositions of the present invention can be prepared, for example, by mixing an active ingredient with a compounding aid. The active ingredient can also be compounded with other aids such as fine solids, mineral oil, vegetable oil or animal oil, modified vegetable oil or modified animal oil, organic solvents, water, surfactants, or combinations thereof.

[0119] One or more active ingredients can also be contained in very fine microcapsules. The microcapsules contain the compound of formula (I) and, optionally, one or more other active ingredients in a porous carrier. This allows for the release of the active ingredients into the environment in a controlled amount (e.g., slow-release). Microcapsules typically have a diameter of 0.1 to 500 microns. They contain the compound of formula (I) and, optionally, one or more other active ingredients in an amount of about 25% to 95% by weight of the capsule weight. The active ingredients may be in the form of a solid mass, fine particles in a solid or liquid dispersion, or a suitable solution. The encapsulation membrane may contain, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane, or chemically modified polymers and xanthogenic starch or other polymers known to those skilled in the art. Alternatively, extremely fine microcapsules can be formed by containing the active ingredient in the form of fine particles within a solid matrix of the base, but the microcapsules themselves are not encapsulated.

[0120] The compounding agents suitable for preparing the compositions according to the present invention are themselves well known.

[0121] As liquid carriers, water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-Heptanone, α-Pinene, d-Limonene, Ethyl Lactate, Ethylene Glycol, Ethylene Glycol Butyl Ether, Ethylene Glycol Methyl Ether, γ-Butyrolactone, Glycerol Acetate, Glycerol Diacetate, Glycerol Triacetate, Hexadecane, Hexylene Glycol, Isoamyl Acetate, Isobornyl Acetate, Isooctane, Isophorone, Isopropylbenzene, Isopropyl Myristate, Lactic Acid, Laurylamine, Mesityl Oxide, Methoxypropanol, Methyl Isoamyl Ketone, Methyl Isobutyl Ketone, Methyl Laurate, Methyl Octanoate, Methyl Oleate, Methylene Chloride, m-Xylene, n-Hexane, n-Octylamine, Octadecanoic Acid, Octylamine Acetate Any of the following can be used: oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, glycerol, N-methyl-2-pyrrolidone, and other high molecular weight alcohols.

[0122] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieslager, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton husk, wheat flour, soy flour, pumice, wood flour, crushed walnut shells, lignin, and similar substances.

[0123] Further auxiliary agents that may be used in formulations include crystallization inhibitors, viscosity modifiers, suspension agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoaming agents, complexing agents, neutralizing agents or pH adjusters and buffers, corrosion inhibitors, fragrances, wetting agents, uptake enhancers, trace elements, plasticizers, lubricants, dispersants, thickeners, antifreezes, fungicides, and liquid and solid fertilizers.

[0124] The composition according to the present invention may contain additives comprising vegetable oil or animal oil, mineral oil, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the present invention is generally 0.01 to 10% based on the mixture applied. For example, the oil additive can be added to the spray tank at a desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or vegetable oil such as rapeseed oil, olive oil, or sunflower oil, emulsified vegetable oil, alkyl esters of vegetable oils such as methyl derivatives, or animal oils such as fish oil or beef tallow. Preferred oil additives include C8 to C 22 Alkyl esters of fatty acids, especially C 12 ~C 18 These are methyl derivatives of fatty acids, including, for example, methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are found in the Compendium of Herbicide Adjuvants, 10 th This information is publicly available from Edition, Southern Illinois University, 2010.

[0125] Commercially available products may preferably be formulated as concentrates, but end users typically utilize diluted formulations.

[0126] The compositions according to the present invention may also contain further solid or liquid additives, such as stabilizers, for example, non-epoxidized or epoxidized vegetable oils (e.g., epoxidized coconut oil, rapeseed oil, or soybean oil), defoamers, for example, silicone oils, preservatives, viscosity modifiers, binders and / or adhesives, fertilizers, or other active ingredients to achieve a particular effect, for example, fungicides, bactericidal and fungicidal agents, antinematodes, plant activators, molluscicides, or herbicides.

[0127] Methods of applying the composition of the present invention, such as by spraying, atomizing, powdering, brushing, coating with powder, scattering, or pouring, that is, methods for controlling the above-mentioned types of pests, and the use of the composition of the present invention for controlling the above-mentioned types of pests are also subjects of the present invention.

[0128] The application rate varies widely and depends on soil properties, application method, crop plants, pests to be controlled, major weather conditions, and other factors that depend on the application method, application timing, and target crop. As a general guideline, the pest-killing composition of the present invention can be applied in amounts of 1 to 2000 l / ha, particularly 10 to 1000 l / ha. The application rate per hectare is generally 1 to 2000 g of active ingredient per hectare, particularly 10 to 1000 g / ha, preferably 10 to 600 g / ha.

[0129] The activity of the pest-killing compositions according to the present invention can be considerably broadened by adding other insecticidal, acaricidal, and / or fungicidal active components to suit general situations. Mixtures of the compound of formula (I) with other insecticidal, acaricidal, and / or fungicidal active components may also have further unexpected advantages, which may be described as synergistic activity in a broader sense. For example, there may be better tolerance by plants, reduced plant toxicity, the ability to control insects at different developmental stages, or better behavior during their manufacture, e.g., during grinding or mixing, during storage, or during use.

[0130] In the field of crop protection, the preferred method of application is application to the stems and leaves of the plant (foliar application), and the frequency and amount of application can be selected according to the risk of infestation by the relevant pests. Alternatively, the active ingredient can reach the plant via the root system (systemic action) by drenching the plant habitat with a liquid composition, or by introducing the active ingredient in solid form into the plant habitat, for example, the soil, in the form of granules (soil application). In the case of rice plants, such granules can be metered and supplied to the paddy field.

[0131] The compositions of the present invention are suitable for protecting plant propagation materials, such as seeds or seedlings of fruits, tubers, or grains, from the above-mentioned types of pests. The propagation material may be treated with this composition before planting; for example, seeds may be treated before sowing. Alternatively, the composition may be applied to seed kernels by immersing them in the liquid composition or by coating them with a layer of the solid composition. If the propagation material is to be planted at the application site, the composition may also be applied between the rows, for example, during drill sowing. These treatment methods for plant propagation materials and the plant propagation materials thus treated are further subjects of the present invention. Typical treatment rates depend on the plant and the pests / fungi to be controlled, and are generally 1 to 200 grams per 100 kg of seeds, preferably 5 to 150 grams per 100 kg of seeds (e.g., 10 to 100 grams per 100 kg of seeds).

[0132] The term "seed" encompasses all types of seeds and plant bulbils, including but not limited to true seeds, seed flakes, suckers, corn kernels, bulbs, fruits, tubers, grains, rhizomes, cuttings, and grafts, and in preferred embodiments, it refers to true seeds.

[0133] The present invention also includes seeds that are coated or treated with or contain a compound of formula (I). The phrase "coated or treated with and / or contain" generally indicates that the active ingredient is, in most cases, on the surface of the seed at the time of application, but depending on the method of application, some of the ingredient may penetrate into the seed material to varying degrees. The active ingredient may be absorbed when the seed product is (re)planted. In one embodiment, the present invention makes available plant propagation material to which a compound of formula (I) has been attached.

[0134] Seed treatment includes all suitable seed treatment techniques known in the art, such as seed powdering, seed coating, seed spraying, seed dipping, and seed pelleting. Seed treatment application of the pesticide composition of the present invention can be carried out by any known method, such as spraying or scattering seeds before sowing or at the time of sowing / planting.

[0135] A further embodiment is a plant propagation material comprising the compound of formula (I) and optionally a coloring pigment, obtained by treatment or coating.

[0136] In each aspect and embodiment of the present invention, "consisting essentially" and its conjugations are preferred embodiments of "comprising" and its conjugations, and "consisting of" and its conjugations are preferred embodiments of "consisting essentially of" and its conjugations.

[0137] The disclosures in this application make available each of the embodiments disclosed herein, and all combinations thereof.

[0138] The following embodiments further illustrate the present invention without any particular limitations. [Examples]

[0139] Example 1 An aqueous, fluid concentrate for seed treatment according to the present invention, containing the compound of formula (I) as an active ingredient, was prepared according to the following formulation.

[0140] [Table 3]

[0141] The above ingredients were blended as follows: (1) Prepare xanthan gum gel; (2) Prepare an aqueous mill base containing the compound of formula (I); (3) The mill base from (1) is ground to a fine particle size using a wet bead mill; and (4) Add the remaining ingredients and mix until a homogeneous composition is obtained.

[0142] A non-limiting example of an ethylene oxide and propylene oxide block copolymer of formula (II) suitable for use in the pesticide composition of Example 1 is, for example, a surfactant commercially available under the trade name PLURONIC® F68.

[0143] Example 2 A seed treatment aqueous fluid concentrate containing the compound of formula (I) as an active ingredient was prepared according to the method described in Example 1, but without using clay (Composition 2).

[0144] Comparative Example 1 A seed treatment aqueous fluid concentrate containing the compound of formula (I) as an active ingredient was prepared according to the method described in Example 1, but the ethylene oxide and propylene oxide block copolymer of formula (II) was HO-(CH2CH2O) 61 -(CH(CH3)CH2O) 40 -(CH2CH2O) 61 -H replaced (wherein the formula, the polyoxyethylene:polyoxypropylene chain length ratio is outside the range of 4:1 to 7:1) (Comparative composition 1):

[0145] [Table 4]

[0146] A non-limiting example of an ethylene oxide and propylene oxide block copolymer suitable for use in the pest-killing composition of Comparative Example 1 is, for example, a surfactant commercially available under the trade name PLURONIC® F87.

[0147] Comparative Example 2 A seed treatment aqueous fluid concentrate containing the compound of formula (I) as an active ingredient was prepared according to the method described in Example 1, but the ethylene oxide and propylene oxide block copolymer of formula (II) was used as HO-(CH2CH2O)8-(CH(CH3)CH2O) 50 -(CH2CH2O)8-H replaced (wherein the formula, the polyoxyethylene:polyoxypropylene chain length ratio is outside the range of 4:1 to 7:1) (Comparative composition 2):

[0148] [Table 5]

[0149] A non-limiting example of an ethylene oxide and propylene oxide block copolymer suitable for use in the pest-killing composition of Comparative Example 2 is, for example, a surfactant commercially available under the trade name PLURONIC® L92.

[0150] Comparative Example 3 A seed treatment aqueous fluid concentrate containing the compound of formula (I) as an active ingredient was prepared according to the method described in Example 1, but the ethylene oxide and propylene oxide block copolymer of formula (II) was HO-(CH2CH2O) 19 -(CH(CH3)CH2O) 39 -(CH2CH2O) 19 -H replaced (wherein the formula, the polyoxyethylene:polyoxypropylene chain length ratio is outside the range of 4:1 to 7:1) (Comparative composition 3):

[0151] [Table 6]

[0152] A non-limiting example of an ethylene oxide and propylene oxide block copolymer suitable for use in the pest-killing composition of Comparative Example 3 is, for example, a surfactant commercially available under the trade name PLURONIC® P84.

[0153] Comparative Example 4 A seed treatment aqueous fluid concentrate containing the compound of formula (I) as an active ingredient was prepared according to the method described in Example 1, but without using ethoxylated lignosulfonate sodium salt (comparative composition 4).

[0154] A sample of one of the compositions from Example 1, Example 2, and Comparative Examples 1-4 was poured into a cup, and the test was performed by visually inspecting whether any precipitate remained at the bottom of the cup. The results are shown in Table 1 below.

[0155] Comparative Example 5 A seed treatment aqueous fluid concentrate containing the compound of formula (I) as an active ingredient was prepared according to the method described in Example 1, but the ethylene oxide and propylene oxide block copolymer of formula (II) was HO-(CH2CH2O) 127 -(CH(CH3)CH2O) 48 -(CH2CH2O) 127 -H replaced (wherein the formula the polyoxyethylene:polyoxypropylene chain length ratio is in the range of 4:1 to 7:1, but x and x' are integers outside the range of 70 to 120, and y is an integer outside the range of 20 to 45) (Comparative composition 5):

[0156] [Table 7]

[0157] A non-limiting example of an ethylene oxide and propylene oxide block copolymer suitable for use in the pest-killing composition of Comparative Example 5 is, for example, a surfactant commercially available under the trade name PLURONIC® F108.

[0158] As shown in Table 1, the sedimentation index is an integer between 1 and 5, taking into account the long-term physical stability of the formulation during storage. An index of 5 indicates that the formulation is perfectly homogeneous during storage. An index of 3 or higher has the advantage of exhibiting good stability, as the formulation can be easily re-homogenized by shaking the sample up to 5-10 times. An index of 1 or 2 unfortunately indicates that the formulation exhibits a high sedimentation rate and settles at the bottom of the cup.

[0159] For example, the pest-killing compositions of the present invention, including composition 1 of Example 1 and composition 2 of Example 2, exhibit an improved precipitation profile compared to comparative compositions 1, 2, and 3, which contain a block copolymer of ethylene oxide and propylene oxide of formula (II) where the polyoxyethylene:polyoxypropylene chain length ratio is outside the range of 4:1 to 7:1 (see Comparative Examples 1 to 3).

[0160] For example, the pest-killing composition of the present invention, which includes composition 1 of Example 1, further exhibits easier rehomogenization of precipitation in the presence of additional clay with additional heteropolysaccharides, compared to composition 2 of Example 2, which does not contain clay.

[0161] For example, the pest-killing composition of the present invention, which includes composition 1 of Example 1 and composition 2 of Example 2, also exhibits better crystallization inhibition properties compared to comparative composition 4 of Comparative Example 4, which does not contain ethoxylated lignosulfonate sodium salt. While comparative composition 4 exhibits good stability performance, it undergoes crystal growth during storage compared to compositions 1 and 2, resulting in undesirable clouding.

[0162] [Table 8] Another aspect of the present invention may be as follows: [1] (a) Compounds of formula (I):

change

change

[10] (a) 10% to 75% by weight of the compound of formula (I), or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, based on the total weight of the composition; (b) 10% to 65% by weight of water based on the total weight of the composition; (c) The surfactant system in an amount of 1% to 25% by weight, based on the total weight of the composition; (d) at least one type of clay in an amount of 0.1% to 2% by weight, based on the total weight of the composition; and (e) 0.05% to 1% by weight of at least one heteropolysaccharide based on the total weight of the composition A composition according to any one of the above items [1] to [9], comprising:

[11] (a) 25% to 60% by weight of the compound of formula (I), or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, based on the total weight of the composition; (b) 25% to 60% by weight of water based on the total weight of the composition; (c) The surfactant system in an amount of 2% to 15% by weight, based on the total weight of the composition; (d) at least one type of clay in an amount of 0.5% to 1.5% by weight, based on the total weight of the composition; and (e) 0.05% to 0.15% by weight of at least one heteropolysaccharide based on the total weight of the composition. A composition according to any one of the above items [1] to

[10] , comprising:

[12] (a) 40% to 60% by weight of the compound of formula (I), or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, based on the total weight of the composition; (b) 30% to 50% by weight of water based on the total weight of the composition; (c) The surfactant system in an amount of 4% to 10% by weight, based on the total weight of the composition; (d) at least one type of clay in an amount of 0.08% to 1.2% by weight, based on the total weight of the composition; and (e) 0.06% to 0.15% by weight of at least one heteropolysaccharide based on the total weight of the composition. A composition according to any one of the above items [1] to

[11] , comprising:

[13] A method for controlling insects, mites, nematodes, or mollusks, comprising applying an effective amount of any one of the above items [1] to

[12] of a pest-killing composition to a pest, a habitat of a pest, a plant susceptible to attack by a pest, or the plant's reproductive material.

[14] The method according to

[13] , wherein the plant is selected from the group consisting of cereals, vegetables, crops, oilseed crops, fodder crops and fiber crops.

[15] Use of any one of the above items [1] to

[12] as an insecticide, acaricide, nematicide, or molluscicide.

Claims

1. A pest-killing composition, (a) A compound of formula (I) in an amount of 40% to 60% by weight based on the total weight of the composition: 【Chemistry 1】 Or, its agriculturally acceptable salts, stereoisomers, enantiomers, tautomers, or N-oxides; (b) 30% to 50% by weight of water based on the total weight of the composition; (c) At least one block copolymer of ethylene oxide and propylene oxide of formula (II): HO-(CH) 2 CH 2 O) x -(CH(CH 3 )CH 2 O) y -(CH) 2 CH 2 O) x’ -H (II) (In the formula, x and x' are either equal to or different from each other, and are integers between 70 and 120. y is an integer between 20 and 45. The chain length ratio of polyoxyethylene to polyoxypropylene is 4:1 to 7:

1. and At least one alkoxylated lignosulfonate of formula (III): 【Chemistry 2】 (In the formula, R 1 , R 2 and R 3 They are either equal to or different from each other, -CH 2 CH 2 -, -CH(CH 3 )CH 2 - and -CH 2 CH 2 CH 2 CH 2 - Selected independently of, i, j, and k are either equal to or different from each other, and are integers from 0 to 15, provided that at least one of i, j, and k is not 0. X is either sodium or potassium. A surfactant system comprising 4% to 10% by weight, based on the total weight of the composition; (d) at least one type of clay in an amount of 0.08% to 1.2% by weight based on the total weight of the composition; and (e) At least one heteropolysaccharide in an amount of 0.06% to 0.15% by weight, based on the total weight of the composition. A pest-killing composition containing the following:

2. In the block copolymer of ethylene oxide and propylene oxide of formula (II), x and x' are either equal to or different from each other, and are integers between 75 and 85. y is an integer between 25 and 35, and The composition according to claim 1, wherein the polyoxyethylene:polyoxypropylene chain length ratio is 5:1 to 6:

1.

3. In the block copolymer of ethylene oxide and propylene oxide of formula (II), x and x' are either equal to or different from each other, and are integers between 75 and 80. y is an integer between 25 and 30, and The composition according to claim 1 or claim 2, wherein the polyoxyethylene:polyoxypropylene chain length ratio is 5:1 to 6:

1.

4. The composition according to any one of claims 1 to 3, wherein the polyoxyethylene:polyoxypropylene chain length ratio is 5.1:1 to 5.5:

1.

5. In the alkoxylated lignosulfonate of formula (III), R 1 , R 2 and R 3 Either of the following is -CH 2 CH 2 If so, i, j, and k are either equal to or different from each other, and are integers between 1 and 12, or R 1 , R 2 and R 3 Either of the following is -CH(CH 3 )CH 2 If so, i, j, and k are either equal to or different from each other, and are integers between 1 and 6, or R 1 , R 2 and R 3 Either of the following is -CH 2 CH 2 CH 2 CH 2 If - then i, j, and k are either equal to or different from each other, and are integers between 1 and 3. R 1 , R 2 and R 3 The composition according to any one of claims 1 to 4, wherein the elements are equal to or different from each other.

6. The aforementioned surfactant system is: Based on the total weight of the surfactant system, 35% to 40% by weight of at least one polyoxyethylene-polyoxypropylene block copolymer of formula (II); and Based on the total weight of the surfactant system, 60% to 65% by weight of at least one alkoxylated lignosulfonate of formula (III) is added. A composition according to any one of claims 1 to 5, comprising:

7. The composition according to any one of claims 1 to 6, wherein the weight ratio of at least one type of clay (d) to at least one type of heteropolysaccharide (e) is 8:1 to 15:

1.

8. The composition according to any one of claims 1 to 7, wherein the weight ratio of at least one type of clay (d) to at least one type of heteropolysaccharide (e) is 9:1 to 10:

1.

9. A method for controlling insects, mites, nematodes, or mollusks in crops, comprising applying 1 to 2000 l / ha of an insecticidal, acaricidal, nematodicidal, or molluscicidal amount of the pesticide composition according to any one of Claims 1 to 8 to a pest, the habitat of the pest, a plant susceptible to attack by the pest, or the plant's reproductive material.

10. The method according to claim 9, wherein the plant is selected from the group consisting of cereals, vegetables, crops, oilseed crops, fodder crops and fiber crops.

11. The use of the pest-killing composition according to any one of claims 1 to 8 as an insecticide, acaricide, nematicide, or mollusk killer, excluding methods for treating humans.

Images