ES2356640T3 - ANTRANILAMIDE, PROCEDURE FOR THE PRODUCTION OF THE SAME AND ANTIPARASITARY AGENTS CONTAINING THE SAME. - Google Patents

Abstract

N- [2-Bromo-4-chloro-6 - [[-methyl- (cyclopropylmethyl) amino] carbonyl] phenyl] -3-bromo-1- (3-chloro-2-pyridyl) -1Hpyrazol-5-carboxamide or its salt or the N-oxide thereof.

Description

TECHNICAL FIELD

[0001] Patent documents 1, 2, 3 and 4, respectively, describe anthranilamide compounds having certain specific chemical structures. However, nowhere in said patent documents are described compounds having an alkyl substituted by a C3-C4 cycloalkyl as substituent 5 corresponding to A in the formula (I) that is represented below in the present invention.

[0002] Also, in patent document 5, anthranilamide compounds having a cyano group at the 4-position of the benzene ring are described. However, in the definition of R1 of the formula (I) depicted below of the present invention, a cyano group is not contained, and the corresponding chemical structures are different. 10

Patent document 1: International publication WO03 / 24222

Patent document 2: International publication WO03 / 15518

Patent document 3: International publication WO03 / 15519

Patent document 4: International publication WO01 / 70671

Patent document 5: International publication 15

DESCRIPTION OF THE INVENTION

PROBLEMS THAT ARE SOLVED WITH THE INVENTION

[0003] For many years, many pesticides have been used, but many of them involve various problems, such as that the effects are inadequate, their use is restricted because pests have acquired resistance, etc. Therefore, it is desirable to develop a new pesticide substantially free of these problems, such as a pesticide capable of controlling various pests that create problems in the fields of agriculture and horticulture and with which parasitic pests can be controlled in animals.

MEANS TO SOLVE THE PROBLEMS

[0004] The authors of the present invention have carried out various studies on anthranilamide compounds in an effort to find a superior pesticide. As a result, they have observed that a new anthranilamide compound or salt thereof has an extremely high pesticidal effect against pests at a low dose, and they have completed the present invention.

 Specifically, the present invention relates to an anthranilamide compound represented by the following formula (I) or a salt thereof:

 30

wherein R1 is a bromine atom substituted at the 2- position of the benzene ring and a chlorine atom substituted at the 4- position of the benzene ring; each R2 is a bromine atom; R3 is a chlorine atom substituted at position 3- of the pyridine ring. A is –CH (Me) -Y; And it is cyclopropyl; m is 2; n is 0 or 1; and q is 1; a process for its production and a pesticide that contains it.

EFFECTS OF THE INVENTION 35

[0005] The pesticide containing as active ingredient the new anthranilamide compound represented by the formula (I) above has a high pesticide effect against pests at a low dose.

BEST MODE FOR CARRYING OUT THE INVENTION

[0006] The number of substituents Y in A is 1. The cycloalkyl of C3 in Y is unsubstituted.

[0007] The salt of the anthranilamide compound of the formula (I) above includes all types, as long as they are agriculturally acceptable. For example, an alkali metal salt, such as sodium salt or potassium salt, may be mentioned; an alkaline earth metal salt such as magnesium salt or a calcium salt; an ammonium salt, such as dimethylammonium salt or a triethylammonium salt, an inorganic acid salt such as a hydrochloride, a perchlorate, a sulfate or a nitrate, or an organic acid salt, such as an acetate or a 5 methanesulfonate

[0008] The anthranilamide compound of formula (I) may have optical isomers or geometric isomers, and said isomers and mixtures thereof are included in the present invention.

[0009] The anthranilamide compound of the above formula (I), or its salt (hereinafter simply referred to as the compound of the present invention) can be produced through the following reactions (A) and (B) according to usual methods to produce a salt.

[0010] R1, R2, R3, A, m, n and q are as defined above, and Z is a chlorine atom, -OH or a C1-C4 alkoxy.

[0011] In the case where Z is chlorine, the reaction (A) can normally be carried out in the presence of a base. fifteen

[0012] As a base, one or more types can be suitably selected for use, such as among an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide; an alkali metal carbonate, such as sodium carbonate or potassium carbonate; an alkali metal hydride such as sodium hydride or potassium hydride; a tertiary amine such as trimethylamine, triethylamine, triisopropylamine, diisopropylamine, pyridine, 4-dimethylaminopyridine, 2,6-dimethylpyridine, 4-pyrrolidinopyridine, N-methylmorpholine, N, N-dimethylaniline, N, N-diethylaniline, N methylalniline, 1,8 1,8-diazabicyclo [5.4.0] -7-undecene or 1,4-diazabicyclo [2.2.2] octane. The base can be used in an amount between 1 and 5 times more per mole, preferably between 1 and 2.5 times more per mole of the compound of formula (II).

[0013] In the case where Z is a chlorine atom, the reaction (A) can be carried out in the presence of a solvent, as the case requires. The solvent may consist of any solvent, as long as it is an inert solvent for the reaction. For example, one or more types of solvents can be suitably selected for use among an ether such as diethyl ether, ethyl butyl ether, tetrahydrofuran, dioxane or dimethoxyethane; a halogenated hydrocarbon such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane or dichloroethylene; an aromatic hydrocarbon such as benzene, toluene or xylene; a polar aprotic solvent such as acetonitrile, propionitrile, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, dimethylacetamide or N-methylpyrrolidone; an ester such as methyl acetate, ethyl acetate or propyl acetate; and a ketone such as acetone, diethyl ketone, methyl ethyl ketone or methyl isobutyl ketone.

[0014] In the case where Z is a chlorine atom, the reaction (A) can normally be carried out at between -20 and + 60 ° C, preferably between 0 and 30 ° C. The reaction time is usually between about 1 and 24 hours, preferably between about 2 and 12 hours.

[0015] In the case where Z is -OH, the reaction (A) can normally be carried out in the presence of a condensation dehydration agent and a solvent. 5

[0016] The condensation dehydration agent may consist, for example, of a carbodimide, such as N, N'-dicyclohexylcarbodimide, 1,3-diisopropylcarbodiimide, or 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, or others such as 1 , 1'-carbonyl-bis-1H-imidazole, phenyl dichlorophosphate, diethyl phosphorcyanidate, 1,3,5-triaza-2,4,6-triphosforin-2,2,4,4,6,6-hexachloride, cyanuric chloride, isobutyl chloroformate, chlorosulfonyl isocyanate or trifluoroacetic anhydride. 10

[0017] The solvent may consist of any solvent as long as it is inert to the reaction. For example, one or more types can be suitably selected for use among an ether such as diethyl ether, ethyl butyl ether, tetrahydrofuran, dioxane or dimethoxyethane; a halogenated hydrocarbon such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane or dichloroethylene; an aromatic hydrocarbon such as benzene, toluene or xylene; a dipolar aprotic solvent such as acetonitrium, propionitrile, 15 N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, dimethylacetamide or N-methylpyrrolidone; an ester such as methyl acetate, ethyl acetate or propyl acetate; a ketone such as acetone, diethyl ketone, methyl ethyl ketone or methyl isobutyl ketone; an aliphatic hydrocarbon such as pentane, hexane, heptane, octane or cyclohexane.

[0018] In the case where Z is -OH, the reaction (A) can be carried out normally at between -20 and + 60 ° C, preferably between 0 and 30 ° C. The reaction time is usually between about 0.5 and 20 hours, preferably between about 1 and 12 hours.

[0019] In the case where Z is C1-C4 alkoxy, reaction (A) can normally be carried out in the presence of a base and a solvent. As a base, one or more types can be suitably selected for use, for example, between an alkali metal hydride such as sodium hydride or potassium hydride; an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium tert-butoxide; and a tertiary amine such as trimethylamine, triethylamine, triiosopropylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, 2,6-dimethylpyridine, 4-pyrrolidinopyridine, N-methyl morpholine, N, N-dimethylaniline, N, N-N-diethylaniline -N-methylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene or 1,4-diazabicyclo [2.2.2] octane. The base can be used in an amount between 1 and 5 times more per mole, preferably between 1 and 2.5 times more per mole of the compound of formula (II).

[0020] The solvent may consist of any solvent as long as it is inert to the reaction. For example, one or more types can be suitably selected for use among an ether such as diethyl ether, ethyl butyl ether, tetrahydrofuran, dioxane or dimethoxyethane; an aromatic hydrocarbon such as benzene, toluene or xylene; a polar aprotic solvent such as acetonitrile, propionitrile, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, dimethylacetamide or N-methylpyrrolidone and an alcohol such as methanol, ethanol, propanol, n-butanol or tert-butanol. 35

[0021] In the case where Z is C1-C4 alkoxy, reaction (A) can normally be carried out at 0 to 120 ° C, preferably between 20 and 80 ° C. The reaction time is usually between about 0.5 and 24 hours, preferably between about 1 and 12 hours.

[0022] The compound of formula (II) or (III) above may consist of a known compound or may be produced in accordance with known reference materials. For example, the compound of formula (II) can be produced through or according to the method described in Synthesis, 1980, p. 505. The compound of formula (III) can be produced through, or according to the method described in schemes 9 to 22 of WO 03/24222.

[0023] R1, R2, R3, A, m, n and q are as defined above.

[0024] The reaction (B) can normally be carried out in the presence of a solvent.

[0025] The solvent may consist of any solvent as long as it is inert to the reaction. For example, one or more types of solvent can be suitably selected for use from an ether such as diethyl ether, ethyl butyl ether, tetrahydrofuran, dioxane or dimethoxyethane; a halogenated hydrocarbon such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane or dichloroethylene; an aromatic hydrocarbon such as benzene, toluene or xylene; and a dipolar aprotic solvent such as acetonitrile, propionitrile, N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane, dimethylacetamide, or N-methylpyrrolidone. 10

[0026] The reaction (B) can normally be carried out at between 0 and 120 ° C, preferably between 20 and 80 ° C. The reaction time is usually between 0.5 and 24 hours, preferably between about 1 and 12 hours.

[0027] The compound of the formula (IV) above may consist of a known compound or may be produced according to the known reference material. For example, the compound of formula (IV) can be produced through or according to the method described in Org. Prep. Proceed Int. 1993, vol. 25 p. 585 or the method described in Schemes 8 to 10 in WO03 / 24222.

[0028] The compound of the formula (V) above includes a new compound. Said compound can be produced through Gabriel's method, and can be produced for example according to the following reaction (C):

 twenty

[0029] In reaction (C), A is defined as above and T is a halogen, -OSO2G (G is a sulfonate radical) or -OH. When T is halogen or –OSO2G, M is sodium or potassium, and when T is –OH, M is a hydrogen atom. He

The sulphonate radical mentioned may consist, for example, of a C1-C6 alkyl, such as methyl or ethyl; or phenyl which may be substituted with a C1-C6 alkyl.

[0030] In the case where T is halogen or -OSO2G and M is sodium or potassium, the first stage of reaction (C) can normally be carried out in the presence of a solvent.

[0031] The solvent may consist of any solvent as long as it is inert to the reaction. For example, one or more types can be suitably selected for use, such as, for example, ether such as diethyl ether, ethyl butyl ether, tetrahydrofuran, dioxane or dimethoxyethane, an aromatic hydrocarbon, such as benzene, toluene or xylene; a dipolar aprotic solvent, such as acetonitrile, propionitrile, N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane, dimethylacetamide or N-methylpyrrolidone; and an alcohol such as methanol, ethanol, propanol, n-butanol or tert-butanol. 10

[0032] In the case where T is halogen or -OSO2G and M is sodium or potassium, the first stage of reaction (C) can normally be carried out at 0 to 150 ° C, preferably between 30 and 110 ° C. The reaction time is usually between about 0.5 and 24 hours, preferably between about 1 and 12 hours.

[0033] In the case where T is -OH and M is a hydrogen atom, the first stage of reaction (C) can normally be carried out through the Mitsunobu method. For example, it can be carried out using an azo dicarboxylate of dialkyl and triphenylphosphine in the presence of a solvent. Each of said azo dialkyl dicarboxylate and triphenylphosphine can normally be used in an amount approximately equimolar to that of the compound of formula (VI). The aforementioned dialkyl dicarboxylate may consist, for example, of diethyl azo dicarboxylate or diisopropyl azo dicarboxylate. twenty

[0034] The solvent may consist of any solvent as long as it is inert to the reaction. For example, one or more types can be suitably selected for use among ethers such as diethyl ether, ethyl butyl ether, tetrahydrofuran, dioxane or dimethoxyethane; a halogenated hydrocarbon such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane or dichloroethylene; an aromatic hydrocarbon such as benzene, toluene or xylene. 25

[0035] In the case where T is -OH and M is a hydrogen atom, the first reaction stage (C) can normally be carried out at a temperature between 0 and 80 ° C, preferably between 20 and 60 ° C. The reaction time is usually between about 0.5 and 24 hours, preferably between about 1 and 16 hours.

[0036] The second stage of reaction (C) can normally be carried out by decomposing compound 30 of formula (VIII) by means of hydrazine in the presence of a solvent. Said hydrazine can be used in an amount approximately equimolar to that of the compound of formula (VIII).

[0037] The solvent may consist of any solvent as long as it is inert to the reaction. For example, one or more types can be suitably selected for use among an ether such as diethyl ether, ethyl butyl ether, tetrahydrofuran, dioxane or dimethoxyethane; an aromatic hydrocarbon such as benzene, toluene or xylene; and an alcohol such as methanol, ethanol, propanol, n-butanol or tert-butanol.

[0038] The second reaction step (C) can normally be carried out at between 0 and 140 ° C, preferably between 30 and 100 ° C. The reaction time is usually between about 0.5 and 24 hours, preferably between about 2 and 12 hours.

[0039] Next, preferable embodiments of the pesticides containing the compound of the present invention will be described. Pesticides containing the compounds of the present invention are particularly useful, for example, as agents for controlling various pests that can become problematic in the agricultural and horticultural fields, that is, agricultural and horticultural pesticides, or as agents for controlling pests that they are parasites in animals, that is, pesticides against parasites in animals.

[0040] Agricultural and horticultural pesticides containing the compounds of the present invention are useful as insecticides, acaricides, nematocides and soil pesticides, and are effective in controlling parasitic mites of plants, such as red spider mites (Tetranychus urticae), Carmine spider mite (Tetranychus cinnabarinus), Kanzawa spider (Tetranychus kanzawai), citrus red mite (Panonychus citri), European red mite (Panonychus ulmi), broad mite (Polyphagotarsonemus latus), rose citrus rust mite (Aculops pelekass) , bulb mite (Rhizoglyphus echinopus), pests of agricultural insects such as diamond back palomilla (Plutella xylostella), 50 cabbage noctuido (Mamestra brassicae), gray tobacco worm (Spodoptera litura), apple tree pine (Laspeyresia pomonella), acorn worm (Heliothis zea), tobacco worm (Heliothis virescens), gypsy palomilla (Lymantria dispar), leaf bender worm (Cnaphalocrocis medinalis) , Adoxophyes sp. stone fruit tortrix (Adoxophyes orana fasciata), peach moth (Carposina niponensis), eastern peach moth (Grapholita molesta), cutworm (Agrotis ipsilon), gray worm (Agrotis segetum), striped potato beetle 55 (Leptinotarsa decemilineata), leaf beetle (Aulacophora femoralis), cotton bill weevil (Anthonomus grandis), aphids, grasshoppers, crickets, bedbugs, whiteflies, thrips, lobsters, antromillid flies, beetles, ants, borers; plant parasitic nematodes, such as root nematodes,

cyst nematodes, nematodes that attack the roots, white rice nematodes (Aphelenchoides besseyi), strawberry nematode (Nothotylenchus acris), pine nematode (Bursaphelenchus lignicolus), gastropods such as slugs and snails; Soil pests such as isopods such as small bug (Armadilidium vulgare), and ball bugs (Portcellio scaber), hygienic insect pests such as tropical rat mite (Ornithonyssus bacoti), common fly (Musca domestica), common mosquito (Culex pipiens), and cockroaches; insect pests of grain 5 stored as cereal popcorn (Sitotroga cerealella), southern bean weevil (Callosobruchus chinensis), brown flour weevil (Tribolium castaneum) and mealworms; moths, household pests and household insect pests, such as suitcase moths (Tinea pellionella), carpet beetles (Anthrenus scrophularidae) and underground termites; domestic mites such as mold mite (Tyrophagus putrescentiae), Dermatophagoides farinae and Chelacaropsis moorel. Among them, agricultural and horticultural pesticides 10 containing the compounds of the present invention are particularly effective in controlling parasitic mites of plants, pests of agricultural insects, parasitic nematodes of plants and the like. They are also effective against insect pests that have acquired resistance against organophosphorus, synthetic pyrethroid and / or carbamate insecticides. Likewise, the compounds of the present invention have excellent systemic properties, and through the application of the compounds of the present invention for soil treatment, not only harmful insects, harmful mites, harmful nematodes, harmful gastropods and isopods can be controlled Harmful on the ground, but also leaf pests.

[0041] Other preferable embodiments of pesticides containing the compounds of the present invention may be agricultural or horticultural pesticides with which the parasitic mites of the plants, the pests of agricultural insects, the parasitic nematodes of the plants are collectively controlled. plants, gastropods and soil pests 20 that have been mentioned before.

[0042] The agricultural and horticultural pesticide containing the compound of the present invention is normally formulated by mixing the compound with various agricultural adjuvants and is used in the form of a formulation such as, for example, powders, granules, water dispersible granules, wettable powders , water-based suspension concentrates, oil-based suspension concentrates, water soluble granules, emulsifiable concentrates, soluble concentrates, pastes, aerosols or an ultra low volume formulation. However, as long as it is suitable for the purposes of the present invention, it can be formulated in any type of formulation that is commonly used in this field. Such agricultural adjuvants include solid vehicles such as diatomaceous earth, dead lime, calcium carbonate, talc, white coal, kaolin, bentonite, a mixture of kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, mirabilite, zeolite and starch; solvents such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and alcohol; extension agents and anionic surfactants such as fatty acid salt, benzoate, alkylsulfosuccinate, dialkylsulphosuccinate, polycarboxylate, alkyl sulfuric acid ester salt, alkyl sulfate, alkylaryl sulfate, alkyl diglylic ether ether sulfate, alcohol sulfuric acid ester salt, alkyl sulfonate, alkylaryl sulfonate, aryl sulfonate, 35 lignin sulfonate, alkyl diphenyl ether disulphonate, polystyrene sulphonate, alkyl phosphoric acid ester salt, alkylaryl phosphate, styrylaryl phosphate, polyoxyethylene alkyl ether sulfuric acid ester salt , polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether sulfuric acid ester salt, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl ether phosphoric acid ester salt, and a formalin naphthalene sulfonate condensate salt ; extension agents and non-ionic surfactants such as sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid polyglyceride, polyglycol fatty acid alcohol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, ether polyoxyethylene alkyl, polyoxyethylene alkylaryl ether, polyoxyethylene styrylaryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyl glycine ethylene hydroxy fatty acid ester polyoxyethylene, polyoxypropylene fatty acid ester, and vegetable oils 45 and minerals such as olive oil, ceiba pentandra oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, oil Flaxseed, tung oil and liquid paraffins. Each of said components, as such adjuvants, may consist of one or more of them properly selected for use as long as the purpose of the present invention can be fulfilled. Also, various additives such as those commonly used, such as fillers, thickeners, anti-settling agents, anti-freezing agents, dispersion stabilizers, agents for reducing phytotoxicity, and anti-mold agents, can also be used.

[0043] The weight ratio of the compound of the present invention and the various agricultural adjuvants is usually between 0.001: 99.9999 and 95: 5, preferably between 0.005: 99.995 and 90:10. 55

[0044] In the actual application of said formulation, it can be used as such or it can be diluted to a previously determined concentration with a diluent such as water, and various extension agents; e.g. Surfactants, vegetable oils or mineral oils may be added, as the case requires.

[0045] The application of the agricultural and horticultural pesticide containing the compound of the present invention cannot be defined in a general way, since it varies depending on the weather conditions, the type of formulation, the season in which it is applied, the Place of application or types or degree of outbreak of pest insects. However, it is usually applied at a concentration of the active ingredient between 0.05 and 800,000 ppm,

preferably between 0.5 and 500,000 ppm, and the dose per unit area is adequate so that the compound of the present invention is between 0.05 and 50,000 g, preferably between 1 and 30,000 g, per hectare. On the other hand, agricultural and horticultural pesticides, as another preferable embodiment of pesticides containing the compounds of the present invention, can be applied according to the pesticide application modes described. The present invention includes such methods for the control of pests, in particular for the control of parasitic mites of plants, pests of agricultural insects or parasitic nematodes of plants through said application forms.

[0046] Various formulations of agricultural and horticultural pesticides containing the compounds of the present invention or their diluted compositions can be applied through conventional methods for their application that are commonly employed, such as spraying (eg, sprayed, sprayed, spray) , atomization, dispersion or spread of dusts or grains in water), application on the ground (eg, mixed or soaked), application on the surface (eg, coating, spraying or coating) or impregnation to poison food. It is also possible to feed domestic animals with food containing the active ingredient mentioned and control the outbreak or development of the pest, particularly insect pests, with their feces. On the other hand, the active ingredient can also be applied through what is called the ultra low volume application method. In this method, the composition may consist of 100% of the active ingredient.

[0047] Likewise, agricultural and horticultural pesticides containing the compounds of the present invention may be mixed or used in combination with other agricultural chemicals, fertilizers or agents to reduce phytotoxicity, whereby effects can be achieved or synergistic activities at times. Such agricultural chemicals include for example herbicides, insecticides, acaricides, nematocides, soil pesticides, fungicides, antiviral agents, baits, antibiotics, plant hormones and plant growth regulating agents. Especially, with a mixed pesticide having the compound of the present invention mixed or used in combination with one or more of the active compounds of another agricultural chemical, the application range, application time, pesticide activities etc. can be improved. ., in the preferable direction. The compound of the present invention and the active compounds of another 25 agricultural chemicals can be formulated separately in order to be able to mix them for use at the time of application, or they can be formulated in combination. The present invention includes said mixed pesticidal composition.

[0048] The mixing ratio of the compound of the present invention and the active compounds of other agricultural chemicals cannot be defined in general, since it varies depending on the weather conditions, the types of formulations, the time of application, the place of application, the types and degree of outbreak of insect pests, etc. but normally it is within the range of 1: 300 to 300: 1, preferably between 1: 100 and 100: 1, by weight. Also, the dose for application is adequate so that the total amount of active compounds is between 0.1 and 50,000 g, preferably between 1 and 30,000 g per hectare. The present invention includes a method for controlling pests through the application of said mixed pesticide composition.

[0049] The active compounds of insect pest control agents such as insecticides, acaricides, nematocides or soil pesticides in the various agricultural chemicals mentioned above include for example (according to common names, some of them are still in the application stage) organic phosphate compounds such as Profenofos, Dichlorvos, Fenamiphos, Fenitrotion, EPN, Diazinon, Chlorpyrifosmethyl, Acetate, 40 Protiofos, Phostiazato, Phosphocarb, Cadusafos, Disulfoton, Chlorpyrifos, Demeton-S-methyl, Dimethoate and Metamid ; Carbamate compounds such as Carbaryl, Propoxur, Aldicarb, Carbofuran, Thiodicarb, Metomil, Oxamyl, Etiofencarb, Pirimicarb, Fenobucarb, Carbosulfan, and Benfuracarb; Nereistoxin derivatives such as Cartap and Tiociaclam and Bensultap; organic chlorine compounds such as Dicofol, Tetradifon and Endosulfan; organimetallic compounds such as fenbutatin oxide; pyrethroid compounds such as Fenvalerate, Permethrin, Cypermethrin, Deltamethrin, Cyhalotrine, Teflutrin, Etofenprox, Fenpropatrin and Biphentrine; benzoyl urea compounds such as Diflubenzuron, Chlorfluazuron, Teflubenzuron, Flufenoxuron, Lufenuron, Novaluron, Bistrifluron and Noviflumuron; juvenile hormone type compounds such as Methoprene, Pyriproxyphene and Phenoxycarb; pyridazinone compounds such as pyridaben; Pyrazole compounds such as Fenpyroximate, Fipronil, Tebufenpirad, Etiprol, Tolfenpirad, Acetoprol, Pirafluprol and Pyriprol; neonicotinoids such as Imidacloprid, Nitenpiram, Acetamiprid, Thiacloprid, Thiamethoxam, 50 Clothianidine and Dinotefuran; hydrazine compounds such as Tebufenozide, methoxyphenozide, Clomaphenozide and Halofenozide, dinitro compounds; organic sulfur compounds; urea compounds; triazine compounds; hydrazone compounds; and other compounds such as Flonicamid, Buprofezin, Hexythiazox, Amitraz, Chlordimeform, Silafluofen, Triazamate, Pymetrozine, Pyrimidifen, Chlorfenapyr, Indoxacarb, Acequinocyl, Etoxazole, Cyromazine, 1,3-dicloropreno, Diafenthiuron, Benclothiaz, Flufenerim, pyridalyl, spirodiclofen, Bifenazate, Spiromesifen, Propargite, 55 Clofentezine, Fluacripirim, Flubendiamide, Cifluometophen, Metaflumizona and Amidoflumet. Also, microbial agricultural chemicals such as BT agents, insect viruses, entomopathogenic fungi and nematophagous fungi, antibiotics such as Avermectin, Emamectin-Benzoate, Mibemectin, Spinosad, Ivermectin and Lepimectin or natural products such as Azadirachtin, and Rotenone can be used in combination or in combination. .

[0050] The active fungicidal compounds among the various agricultural chemicals mentioned include 60 for example (according to common names, some are still in the application stage), pyrimidinamine compounds such as Mepanipirim, Pyrimethanil and Cyprodinyl; Azole compounds such as Triadimefon, Bitertanol,

Triflumizol, Etaconazole, Propiconazole, Penconazole, Flusilazole, Miclobutanil, Ciproconazole, Terbuconazole, Hexaconazole, Furconazole-cis, Prochloraz, Metconazole, Epoxiconazole, Tetraconazole, Oxpoconazole and Sipconazole; Quinoxaline compounds such as Quinomethionate; dithiocarbamate compounds such as Maneb, Zineb, Mancozeb, Polycarbamate, Propineb; organic chlorine compounds such as Ftalida, Chlorothalonil, Quintozeno; imidazole compounds such as Benomil, Thiophanate-Methyl, Carbendazim and Ciazofamid; pyridinamine compounds such as Fluazinam, cyanoacetamide compounds such as Cimoxanil; phenylamide compounds such as Metalaxyl, Oxadixyl, Ofurace, Benalaxyl, Furalaxyl, and Ciprofuram; sulfenic acid compounds such as Diclofluanid; copper compounds such as cupric hydroxide and Oxine Copper; isoxazole compounds such as hydroxyisoxazole; organophosphorus compounds such as Fosetyl-Al, Tolclofos-Methyl, O, S-benzyl O-diisopropylphosphorothioate, S, O-ethyl S-diphenylphosphorodithioact, and aluminomethyl hydrogen phosphonate; N-halogenothioalkyl compounds such as Captano, Captafol and Folpet; 10 dicarboximide compounds such as Procimidone, Iprodione and Vinclozoline; benzanilide compounds such as Flutolanil, Mepronil and Zoxamide; piperazine compounds such as Triforin; pyridine compounds such as Pirifenox; carbinol compounds such as Fenarimol; and Flutriafol; piperidine compounds such as fenpropidine; morpholine compounds such as fenpropimorph; tin organ compounds such as Fentin hydroxide and Fentin acetate; urea compounds such as Pencicuron; cinnamic acid compounds such as Dimetomorph, phenyl carbamate compounds such as Dietofencarb; cyano pyrrole compounds such as Fludioxonil and Fenpiclonil; Estrobilurin compounds such as Azoxystrobin, Kresoxim-methyl, Metominophen; Trifloxystrobin, Picoxystrobin and Pyraclostrobin; oxazolidinedione compounds such as Famoxadone; thiazole carboxamide compounds such as Etaboxam; silyl amide compounds such as Siltiofam; amino acid amidocarbamate compounds such as Iprovalicarb; imidazolidine compounds such as fenamidone; hydroxyanilide compounds such as Fenhexamid; benzene sulfonamide compounds such as Flusulfamide; anthraquinone compounds; crotonic acid compounds; antibiotics and other compounds such as isoprotiolane; Triciclazole, Pyroquilon, Diclomezine, Probenazole, Quinoxilfen; Propamocarb, Spiroxamine, Chloropicrin, Dazomet and Metam-Sodium hydrochloride.

[0051] Likewise, agricultural chemicals that can be used in admixture or in combination with the compounds of the present invention may, for example, consist of compounds that are active ingredients of herbicides such as those described in Farm Chemicals Handbook (2002 edition), in particular those of the type of soil treatment.

[0052] Pesticides against parasites in animals are effective in controlling, eg, external parasites that are parasites on the surface of the host animal's body (such as the back, armpits, lower abdomen or inside the thigh) or parasites internals that are parasites in the body of host animals (such as the stomach, intestinal tract, lungs, heart, liver, blood vessels, subcutaneous or lymphatic tissues), but are especially effective in controlling external parasites .

[0053] External parasites may consist, for example, of mites or parasitic fleas of animals. Their species are so many that it would be difficult to list them all, so only the typical examples are indicated.

[0054] Parasites mites animals can be, for example cattle tick Boophilus microplus, 35 Rhipicephalus sanguineus, Haemaphysalis longicornis, Haemaphysalis flava, Haemaphysalis campanulata, Haemaphysalis concinna, japonica Haemaphysalis, Haemaphysalis kitaokai, ias Haemaphysalis, Ioxodes ovatus, Ixodes nipponensis, Ixodes persulcatus , Amblyomma testudinarium, Haemaphysalis megaspinosa, Dermacentor reticulatus and Dermacentor taiwanensis; common red mites (Dermanyssus gallinae); wild pigeon mites such as Ornithonyssus syviarum and Ornithonyssus bursa; thrombidioids such as Eutrombicula wichmanni, Leptotrombidium 40 akamushi, Leptotrombidium pallidum, Leptotrombidium fuji, Leptotrombidium tosa; Neotrombicula autumnalis, Eutrombicula alfreddugesi and Helenicula miyagawai; cheyletides such as Cheyletiella yasguri, Cheyletiella parasiltivorax and Cheyletiella blakei; Sarcoptic mange mites such as Psoroptes cuniculi, Chorioptes bovis, Otodectes cynotis, Sarcoptes scabiei and Notoedres cati; and Demodicidae as Demodex canis. Pesticides against parasites in animals containing the compounds of the present invention are particularly effective for the control of ticks between them.

[0055] Fleas may consist, for example, of insects without parasitic wings belonging to the Siphonaptera, more specifically fleas belonging to Pulicideae, Ceratephyllus, etc. Fleas belonging to Pulicidae may consist, for example, of Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Echidnophaga gallinacea, Xenopsylla cheopis, Leptosylla segnis, Nosopsyllus fasciatus and Monopsyllus anisus. The 50 pesticides against parasites in animals containing the compounds of the present invention are particularly effective for the control of fleas belonging to the Polyacids, in particular Ctenocephalides canis and Ctenocephalides felis, among them.

[0056] Other external parasites may consist, for example, of chewing lice (Anoplura) such as sucking lice (Haematopinus eurysternus), equine sucking louse (Haematopinus asini), long-nosed cattle louse (Linognathus vituli), and head louse (Pediculus capitis); biting lice, such as dog biting lice (Trichodectes canis); and sucking diptera insects, such as common horsefly (Tabanus trigonus), biting flies (Culicoides schultzei) and black fly (Simulium ornatum). Likewise, internal parasites may consist, for example, of nematodes such as lung worms, tricocephalus (Trichuris), tuber worms, gastric parasites, ascaris, and filarioids; cestodes such as Spirometra erinacei, Diphyllobothrium latum, 60 Dipylidium caninum, Taenia multiceps, Echinococcus granulosus, Echinococcus multilocularis, trematodes such as

Schistosoma japonicum, Fascilola hepatica and protozoa such as coccidia, malaria parasites (Plasmodium malariae), intestinal sarcocysts, toxoplasma and cryptosporidium.

[0057] Animals may consist, for example, of pets, pets and poultry, for example dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (such as pigeons, parrots, mainatá beo, Java sparrow, parrots, doves and canaries), cows, horses, pigs, sheep, ducks and chickens. The pesticides against parasites in animals containing the compounds of the present invention are particularly effective for the control of pest parasites on pet animals or domestic animals, especially for the control of external parasites, among them. Among pet animals and pets are particularly effective for dogs, cats, cows and horses.

[0058] When the compound of the present invention is used as a pesticide against parasites in animals, it can be used as such or can be used with a suitable adjuvant, as formulated in various formulations such as powders, granules, tablets, powders, capsules, soluble concentrates, emulsifiable concentrates, an aqueous-based suspension concentrate and an oil-based suspension concentrate. In addition to such formulations, it can be formulated in any type of formulation that is commonly used in this field, as long as it is suitable for the purposes of the present invention. The adjuvants used in the formulations may consist, for example, of anionic surfactants or non-ionic surfactants, the examples of which have been mentioned above as adjuvants for the formulation of agricultural and horticultural pesticides; a cationic surfactant such as cetyl trimethylammonium bromide; a solvent such as water, acetone, acetonitrile, monomethylacetamide, dimethylacetamide, dimethylformamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, kerosene, triacetin, methanol, ethanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol liquid polyoxyethylene glycol, butyl diglycol, monomethyl ether of ethylene glycol, monoethyl ether of ethylene glycol, monoethyl ether of diethylene glycol, n-butyl ether of diethylene glycol, monomethyl ether of dipropylene glycol, n-butyl ether of dipropylene; an antioxidant such as butylhydroxyanisole, butylhydroxytoluene, ascorbic acid, sodium hydrogen methanesulfite, propyl gallate or sodium thiosulfate; an agent for forming a coating film such as polyvinyl pyrrolidone, polyvinyl alcohol or a copolymer of vinyl acetate and vinyl pyrrolidone; 25 vegetable oils and mineral oils such as those indicated as examples above as formulation aids and agricultural and horticultural pesticides; and a vehicle such as lactose, sucrose, glucose, starch, wheat flour, cornmeal, soybean cake and flour; degreased rice bran, calcium carbonate and other commercially available food materials. One or more of the corresponding components of these adjuvants can be suitably selected for use as long as they do not depart from the purpose of the present invention. Likewise, other adjuvants other than those mentioned among those known in this field can be suitably selected for use, and some of the different adjuvants used in the aforementioned agriculture and horticulture field can also be suitably selected for use.

[0059] The mixing ratio of the compound of the present invention and the various adjuvants is usually between 0.1: 99.9 and 90: 1.0. In the actual use of said formulation, it can be used as such or it can be diluted to a concentration previously determined with a diluent such as water, and various extension agents (eg, surfactants, vegetable oils and mineral oils) can be added, as the case requires.

[0060] Administration of the compound of the present invention to a host animal is carried out orally or parenterally. As the method of oral administration, there can be mentioned a method of administration of a tablet, a liquid agent, a capsule, a wafer, a cookie, crushed meat or other food, containing the compound of the present invention. As a method of parenteral administration, there can be mentioned, for example, a method in which the compound of the present invention is formulated in a suitable formulation and then introduced into the body e.g. by intravenous administration, intramuscular administration, intradermal administration, hypodermic administration, etc .; a method in which it is administered on the surface of the body by one-point treatment, pouring treatment or spray treatment; or a method of embedding a resin fragment or the like containing the compound of the present invention under the skin of the host animal.

[0061] The dose of the compound of the present invention in the host animal varies depending on the method of administration, the purpose of the administration, the symptom of the disease, etc., but is usually administered in a proportion comprised between 0.01 mg. and 100 g, preferably between 0.1 mg and 10 g, for every 1 kg of body weight of the host animal.

[0062] The present invention also includes a pest control method through the aforementioned method of administration or through the aforementioned dose, in particular a method of controlling external parasites or internal parasites.

[0063] Also, in the present invention, it may be the case in which by controlling parasitic pests in the animals, as described, it is possible to prevent or cure the various diseases of the host animal caused by them. Therefore, the present invention also includes a preventive or therapeutic agent for an animal disease caused by a parasite containing the compound of the present invention as an active ingredient, and a method for preventing or curing an animal disease caused by a parasite.

[0064] When the compound of the present invention is used as a pesticide against parasites in animals, several vitamins, minerals, amino acids, nutrients, enzymes, antipyretics, sedatives, antiphlogistics, fungicides dyes, aromatic substances, preservatives, etc., can be used. or in combination with adjuvants. Likewise, as the case requires, other drugs for animals or agricultural products, such as vermicides, anti-coccidium agents, insecticides, acaricides, pulicides, nematocides, bactericides or antibacterial agents, may be mixed or combined for use. which can sometimes get better effects. The present invention includes said mixed pesticidal composition having the various components mentioned above mixed or combined for use, as well as a method for controlling a pest through its use, in particular, a method for controlling external parasites or internal parasites. .

[0065] Next, several preferable embodiments of the compounds of the present invention will be illustrated. In the examples, two or more suitably can be combined, and compounds based on such combinations are also preferable embodiments of the compounds of the present invention. Likewise, preferable embodiments of the present invention are pesticides, pesticides for agriculture and horticulture, insecticides, acaricides, nematocides, pesticides against parasites in animals, pesticides against external parasites in animals and preventive or therapeutic agents for animal diseases caused by parasites. , which contain the following compounds as active ingredients. On the other hand, the methods for controlling pests thus applying effective amounts of the following compounds also with preferable embodiments of the present invention.

EXAMPLES

[0066] Next, the present invention will be described with reference to the examples, but it should be understood that the present invention is not limited at all with them. First, the preparation examples of the compound of the present invention will be described.

PREPARATION EXAMPLE 1 (Reference)

Preparation of N- [6 - [[(cyclopropylmethyl) amino] carbonyl] -2-methylphenyl] -1- (3-chloro-2-pyridyl) -3-trifluoromethyl) -1H-pyrazole-5-carboxamide (hereinafter referred to as compound No. 1) 25

[0067] 1.49 g of triethylamine were gradually added dropwise to a mixed solution comprising 0.8 g of cyclopropylmethylamine hydrochloride and 40 ml of tetrahydrofuran, with ice cooling, followed by stirring at room temperature for 30 minutes. Then, a mixed solution comprising 1 g of 2- [1- (3-chloro-2-pyridyl) -3- (trifluoromethyl) -1 H -pyrazol-5-yl] -8-methyl was gradually added dropwise -4H-3,1-benzoxazin-4-one and 10 ml of tetrahydrofuran. After completion of the dropwise addition, the mixed solution was reacted for 4 hours at reflux. After completion of the reaction, the solvent was distilled off under reduced pressure and ethyl acetate and water for extraction were added to the residue. The organic layer was washed with water and saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by column chromatography on silica gel (eluent: n-hexane / ethyl acetate = 1/1) to obtain 0.54 g of the desired product having a point melting of 199.4 ° C. 35

PREPARATION EXAMPLE 2 (Reference)

Preparation of N- [4-chloro-2-methyl-6 - [[-methyl- (cyclopropylmethyl) amino] carbonyl] -phenyl] -3- (trifluoromethyl) -1- (3-chloro-2-pyridyl) - 1H-pyrazole-5-carboxamide (hereinafter referred to as compound No. 3)

[0068] 1.37 g of triethylamine were gradually added dropwise to a mixed solution comprising 0.82 g of -methyl-cyclopropylmethylamine hydrochloride and 40 ml of tetrahydrofuran, with ice cooling, followed by temperature stirring Ambience for 30 minutes. Then, a mixed solution comprising 1 g of 2- [1- (3-chloro-2-pyridyl) -3- (trifluoromethyl) -1H-pyrazol-5-yl] -6-chloro was added gradually dropwise -8-methyl-4H-3,1-benzoxazin-4-one and 10 ml of tetrahydrofuran. After completion of the dropwise addition, the mixed solution was reacted for 4 hours at reflux. After completion of the reaction, the solvent was distilled off under reduced pressure and ethyl acetate and water were added to the residue. The organic layer was washed with water and saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica gel (eluent: n-hexane / ethyl acetate = 1/1) to obtain 0.45 g of the desired product having a melting point 210.0 ° C.

PREPARATION EXAMPLE 3 (Reference)

Preparation of N- [4-chloro-2-methyl-6 - [[-methyl- (cyclopropylmethyl) amino] carbonyl] -phenyl] -3-bromo-1- (3-chloro-2-pyridyl) -1H- 50 pyrazol-5-carboxamide (hereinafter referred to as compound No. 9)

[0069] 1.07 g of triethylamine were gradually added dropwise to a mixed solution that cp, `remdçoa 0.65 g of -methyl-cyclopropylmethylamine hydrochloride and 40 ml of tetrahydrofuran, with ice cooling, followed by stirring at room temperature for 30 minutes. Then, a mixed solution comprising 0.8 g of 2- [3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazol-5-yl)] 6-chloro was gradually added dropwise -8-methyl-4H-3,1-55 benzoxazin-4-one and 10 ml of tetrahydrofuran. After completion of the dropwise addition, the mixed solution was reacted for 4 hours at reflux. After completion of the reaction, the solvent was distilled off at

reduced pressure and ethyl acetate and water for extraction were added to the residue. The organic layer was washed with water and a saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by column chromatography on silica gel (eluent: n-hexane / ethyl acetate = 1/1) to obtain 0.33 g of the desired product having a point melting of 183.6 ° C. 5

PREPARATION EXAMPLE 4

Preparation of N- [2-bromo-4-chloro-6 - [[-methyl- (cyclopropylmethyl) -amino] carbonyl] -phenyl] -3-bromo-1- (5-chloro-2-pyridyl) -1H -pyrazol-5-carboxamide (hereinafter referred to as compound No. 16)

[0070] 1 g of triethylamine was gradually added dropwise to a mixed solution comprising 0.6 g of -methyl-cyclopropylmethylamine hydrochloride and 40 ml of tetrahydrofuran with ice cooling, followed by stirring for 1 hour at temperature ambient. Then, a mixed solution comprising 0.85 g of 2- [3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazol-5-yl] -6-chloro was gradually added dropwise -8-bromo-4H-3,1-benzoxazin-4-one and 10 ml of tetrahydrofuran. After completion of the dropwise addition, the mixed solution was reacted for 4 hours at reflux. After completion of the reaction, the solvent was distilled off and ethyl acetate and water were added to the residue. The organic layer was washed with water and saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by column chromatography on silica gel (eluent: n-hexane / ethyl acetate = 1/2) to obtain 0.7 g of the desired product having a point melting of 260.6 ° C.

[0071] The following are typical examples of the compound of the present invention represented by the formula (I) above in Table 1. Such compounds can be prepared as in the preparation examples described or through the various production processes of the compound of the present invention mentioned above.

[0072] In Table 1, No. represents compound No. Also, in Table 1, Me represents a methyl group, Et an ethyl group, iPr an isopropyl group, CPr a cyclopropyl group, CBu a cyclobutyl group, and pH a phenyl group. Also, in Table 1, A1 represents -CH2- [CPr], A2 –CH (Me) - [CPr], A3 –CH2- [2-Me-CPr], A4 –CH2- [2,2-Cl2- 1-Me-25 CPr], A5 –CH2- [1-Me-CPr] and A6 –CH (Me) - [CBu]. Also, in Table 1, 2-Me-CPr represents a cyclopropyl group having a substituted methyl group in the -2 position and CO2Ph (4-Cl) represents a phenoxycarbonyl group that has a substituted chlorine atom in position 4- from the phenyl group. The same applies in other similar descriptions.

[0073] On the other hand, in table 1, n is 0 unless otherwise specified.

TABLE 1

 No.

 R1a R1b R1c R1d R2 R3a R3b R3c R3d A Physical properties (mp: ° C)

 one*

 Me H H H CF3 Cl H H H A1 199.4

 2*

 Me H Cl H CF3 Cl H H H A1 216.4

 3*

 Me H Cl H CF3 Cl H H H A2 210.0

 4*

 Me H Cl H CF3 Cl H H H A3

 5*

 Me H Cl H CF3 Cl H H H A4 219.3

 6 *

 Me H Cl H Cl Cl H H H A1

 7 *

 Me H Cl H Br Cl H H H A1

 8 *

 Me H Cl H Cl Cl H H H A2 186.7

 9 *

 Me H Cl H Br Cl H H H A2 183.6

 10 *

 Me H Cl H CF3 Cl H H H A5 161.2

 eleven*

 Br H Cl H CF3 Cl H H H A2 158.2

 12 *

 I H Br H CF3 Cl H H H A2 145.5

 13 *

 Me H Cl H CF3 Cl H H H A2 230.9

 14 *

 Cl H Cl H CF3 Cl H H H A2 238.8

 fifteen*

 Cl H Cl H Br Cl H H H A2 236.8

 16

 Br H Cl H Br Cl H H H A2 260.6

 17 *

 I H Cl H Br Cl H H H A2 251.4

 18 *

 Br H F H CF3 Cl H H H A2 220.1

 19 *

 I H Cl H CF3 Cl H H H A2 241.0

 twenty*

 Cl H F H CF3 Cl H H H A2 214.0

 twenty-one*

 I H I H CF3 Cl H H H A2 251.9

 22 *

 Br H F H Br Cl H H H A2 219.2

 2. 3*

 Me H Cl H CF3 Br H H H A2 162-164

 24 *

 Me H Cl H Cl CF3 H H H A2 154-156

 25 *

 Me H Cl H Br Br H H H A2 128-132

 26 *

 Cl H F H Br Cl H H H A2

 27 *

 I H F H Br Cl H H H A2

 28 *

 F H Cl H Br Cl H H H A2

 29 *

 F H Cl H CF3 Cl H H H A2

 30 *

 I H F H CF3 Cl H H H A2

 No.

 R1a R1b R1c R1d R2 R3a R3b R3c R3d A Physical properties (mp: ° C)

 31 *

 F H F H CF3 Cl H H H A2

 32 *

 F H F H Br Cl H H H A2

 33 *

 Me H F H CF3 Cl H H H A2

 3. 4*

 Me H F H Br Cl H H H A2

 35 *

 Me H CO2Me H Br Cl H H H A2

 36 *

 Me H CO2-iPr H Br Cl H H H A2

 37 *

 Me H CO2Ph H Br Cl H H H A2

 38 *

 Br H Cl H Cl Cl H H H A2 233.2

 39 *

 Br H F H Cl Cl H H H A2 179.1

 40 *

 Me H COCH3 H CF3 Cl H H H A2 143.4

 41 *

 Me H CHO H CF3 Cl H H H A2 152.3

 42 *

 Me H CHF2 H CF3 Cl H H H A2 212.9

 43 *

 Me H CHF2 H Br Cl H H H A2

 44 *

 Me H CHF2 H Cl Cl H H H A2

 Four. Five*

 Et H Cl H CF3 Cl H H H A2 215.4

 46 *

 Et H Cl H Br Cl H H H A2

 47 *

 Et H Cl H Cl Cl H H H A2

 48 *

 Me H NO2 H CF3 Cl H H H A2 197.9

 49 *

 Me H NO2 H Br Cl H H H A2

 fifty*

 Me H NO2 H Cl Cl H H H A2

 51 *

 Me H CF3 H Br Cl H H H A2

 52 *

 Me H CF3 H Cl Cl H H H A2

 53 *

 Me H CF3 H CF3 Cl H H H A2

 54 *

 CF3 H Cl H Br Cl H H H A2

 55 *

 Me H OMe H Br Cl H H H A2

 56 *

 Me H OMe H CF3 Cl H H H A2

 57 *

 Me H OMe H Cl Cl H H H A2

 58 *

 OCHF2 H Cl H Cl Cl H H H A2

 59 *

 OCHF2 H Cl H Br Cl H H H A2

 60 *

 OCHF2 H Cl H CF3 Cl H H H A2

 61 *

 CHF2 H Cl H CF3 Cl H H H A2

 No.

 R1a R1b R1c R1d R2 R3a R3b R3c R3d A Physical properties (mp: ° C)

 62 *

 CHF2 H Cl H Br Cl H H H A2

 63 *

 CHF2 H Cl H Cl Cl H H H A2

 64 *

 Me H CH = CH2 H CF3 Cl H H H A2

 65 *

 Me H C = CH H CF3 Cl H H H A2

 66 *

 Me H Cl H CF3 Cl H H H A2

 67 *

 Me H COCF3 H Br Cl H H H A2

 68 *

 Me H CH = CCl2 H CF3 Cl H H H A2

 69 *

 Me H C = Cl H CF3 Cl H H H A2

 70 *

 Me H CO2Ph (4-Cl) H Br Cl H H H A2

 71 *

 Me H CO2Ph (4-Me) H CF3 Cl H H H A2

 72 *

 Me H CO2Ph (4-NO2) H CF3 Cl H H H A2

 73 *

 Me H CO2Ph (4-CN) H CF3 Cl H H H A2

 74 *

 Me H CO2Ph (4-SMe) H CF3 Cl H H H A2

 75 *

 Et H Cl H OCH2CF3 Cl H H H A2

 76 *

 Me H NO2 H OCH2CF3 Cl H H H A2

 77 *

 Me H CHF2 H CF3 H H Cl H A2

 78 *

 Et H Cl H Br H H F H A2

 79 *

 I H Cl H Br F H F H A2

 80 *

 I H Cl H Cl Cl H H H A2 220.6

 81 *

 Me H Cl H OCH2CF3 Cl H H H A2 175.1

 82 *

 Br H CHF2 H CF3 Cl H H H A2

 83 *

 Br H CHF2 H Br Cl H H H A2

 84 *

 Br H CHF2 H Cl Cl H H H A2

 85 *

 Me H Cl H CF3 Cl H Cl H A2

 86 *

 Me H Cl H CF3 Cl H F H A2

 87 *

 Br H NO2 H Br Cl H H H A2

 88 *

 Br H NO2 H CF3 Cl H H H A2

 89 *

 Br H NO2 H Cl Cl H H H A2

 90 *

 I H Br H Cl Cl H H H A2 222.9

 91 *

 I H Br H Br Cl H H H A2 221.0

 92 *

 Me H Me H CF3 Cl H H H A2 172.3

 No.

 R1a R1b R1c R1d R2 R3a R3b R3c R3d A Physical properties (mp: ° C)

 93 *

 Me H CO2-iPr H Br Cl H H H A2 176-179

 94 *

 Et H Br H CF3 Cl H H H A2 175.2

 95 *

 Et H NO2 H CF3 Cl H H H A2 116.8

 96 *

 Me H CO2Me H Br Cl H H H A2 190-198

 97 *

 CF3 H Cl H Br Cl H H H A2

 98 *

 CF3 H Br H CF3 Cl H H H A2 234.8

 99 *

 CF3 H Cl H CF3 Cl H H H A2 230.0

 100 *

 Cl H CF3 H Br Cl H H H A2

 101 *

 Br H CF3 H CF3 Cl H H H A2

 102 *

 Cl H CF3 H CF3 Cl H H H A2

 103 *

 N-oxide of compound No. 1 (n = 1)

 104 *

 N-oxide of compound No. 3 (n = 1)

 105 *

 N-oxide of compound No. 9 (n = 1)

 106

 N-oxide of compound No. 16 (n = 1)

 107 *

 N-oxide of compound No. 22 (n = 1)

 108 *

 N-oxide of compound No. 42 (n = 1)

 * Reference example

[0074] Next, test examples will be described

TEST EXAMPLE 1

Test on the control of the effects against the common caterpillar (Spodoptera litura) 5

[0075] A pumpkin leaf segment was immersed for approximately 10 seconds in an insecticidal solution prepared to obtain a concentration of the compound of the present invention of 50 ppm or 3.1 ppm and air dried. A wet filter paper was placed in a petri dish having a diameter of 9 cm, and the dried pumpkin leaf segment was placed on top. 10 larvae were released in the second-third instar of common caterpillars in it and after placing a cover, they were left in a chamber at a constant temperature at 25 ° C, with 5 lighting. The dead larvae were counted 5 days after they were released and the mortality was calculated with the following equation. At this point, the dying insects were counted as dead insects. The 50 ppm mortality rate was obtained in relation to the aforementioned compounds No. 8, 20 to 22, 25, 41, 91 to 93 and 96, whereby all the compounds had high control effects with a mortality of at least 90%, and the mortality at 3.1 ppm was obtained in relation to the aforementioned compounds No. 1 to 3, 5, 9 to 10 19, 23, 24, 38 to 40, 42, 80, 81 and 90 , by virtue of which all the compounds had high control effects with a mortality of at least 90%.

Mortality (%) = (number of dead insects /

number of insects released) x 100

TEST EXAMPLE 2 15

Test to control the effects against the whitefly (Bermisia argentifoli)

[0076] Whitefly adults were released in a cucumber with only the first main leaf having cut the other leaves and planted in a pot allowing them to lay eggs for 8 hours. It was then left for 7 to 10 days in a constant temperature chamber at 25 ° C with illumination. The hatching was counted and then, the infested leaf was immersed for approximately 10 seconds in an insecticidal solution prepared to achieve a concentration of the compound of the present invention of 200 ppm or 50 ppm and air dried. After treatment, it was left in a chamber at a constant temperature at 25 ° C with illumination for 10 to 14 days, after which the number of larvae of last instar and the number of pupae was counted and the protection value was obtained with the equation indicated below. The protection value at 200 ppm was obtained with respect to the aforementioned compounds No. 11 and 21, whereby high control effects were demonstrated with a protection value of at least 80% and a value was obtained of protection of 50 ppm with respect to the aforementioned compounds No. 3, 9, 12, 14 to 20, 22, 38 and 39, whereby the compounds had a high control effect with a protection value of at least 80%

Protection value (%) = (1 - ((TaxCb) / (TbxCa))) x100

Ta: number of larvae at last instar + number of pupae after treatment in treated section 30

Tb: number of hatches before treatment in the treated section

Ca: Number of larvae in last instar + number of pupae after treatment in the treated section

Cb: Number of hatches before treatment in the treated section

TEST EXAMPLE 3

Test to control the effects against the green peach aphid (Myzus persicae) 35

[0077] The petiole of an eggplant was covered in which only the main leaf had been left and planted in a pot, with a sticky substance, and then approximately 2-3 green-pea aphid aphidian viviparous females were released on the main leaf . After two days since they were released, the adult insects were removed and the number of larvae was counted. Next, the infested eggplant leaf with the larvae was immersed in an insecticidal solution prepared to obtain a concentration of the compound of the present invention at 800 ppm, for approximately 10 seconds, then air dried and left in a chamber constant temperature at 25ºC with lighting. Insects that survived 5 days after treatment were counted and mortality was calculated using the equation indicated below. The death rate was obtained in relation to the aforementioned compounds No. 2, 9, 11, 14 to 18, 20, 22, 23, 38, 39, 42 and 90, whereby all the compounds had high effects of control with a mortality of at least 45%.

Mortality (5) = (1- (number of surviving insects / number of treated insects)) x 100

TEST EXAMPLE 4

Test to control the effects against cotton aphid (Aphis gossypii)

[0078] The petiole of an eggplant that had only the main leaf was coated with a sticky substance and 50 planted in a pot; then approximately 3-4 apiparous viviparous females of the cotton aphid were released on the main leaf. After two days since they were released, the adult insects were removed and the number of larvae was counted. The infested eggplant leaf with the larvae was immersed in an insecticidal solution prepared to obtain a concentration of the compound of the present invention of 50 ppm, during

approximately 10 seconds, then air dried and left in a constant temperature chamber at 25 ° C with illumination. The number of surviving insects was counted 5 days after treatment and the death rate was obtained in the same manner as in the trial of Example 3 above. The mortality rate was obtained in relation to the aforementioned compounds No. 16, 18 and 22, whereby all the compounds had high control effects with a mortality of at least 90%. 5

TEST EXAMPLE 5

Test to control the effects against the mining fly (Liriomyza trifolli)

[0079] A segment of red bean leaf that had uniformly placed flyfly eggs was immersed on it, for approximately 10 seconds, in an insecticidal solution prepared to obtain a concentration of the compound of the present invention of 25 ppm or 12, 5 ppm, and then air dried. The wet filter paper was placed on a plastic cup that had a diameter of 9 cm and a height of 4 cm, and the dried red bean leaf segment was placed on top. Then, after placing a cover on top, it was left in a constant temperature chamber at 25 ° C with illumination. The number of larvae was last counted and the number of pupae for 6 to 8 days after treatment and the protection value was calculated through the equation indicated below. The protection value at 25 ppm was obtained with respect to the 15 compounds mentioned above No. 9, 14 and 23, whereby all the compounds had high control effects with a protection value of at least 90%, and they were obtained the protection value of 12.5 ppm in relation to the mentioned compounds nº 2, 3, 11, 12, 15 to 18 and 22, whereby the compounds had high control effects with a protection value of at minus 90%

Protection value (%) = (1 - ((number of larvae in last instar + number of pupae in the treated section) / 20 (number of larvae in last instar + number of pupae in the untreated section))) x 100

TEST EXAMPLE 6

Trial to control the effects against Thrips palmi

[0080] All the leaves of a cucumber planted in a pot except the main leaf were cut. The remaining sheet was immersed for approximately 10 seconds in an insecticidal solution prepared to obtain a concentration of the compound of the present invention at 50 ppm and air dried. Next, a segment of the cucumber leaf with larvae was first placed on the previous treated leaf. The next day, the cucumber leaf segment was removed and the number of larvae transferred to the treated leaf was counted. A wet filter paper was placed in a plastic cup that had a diameter of 9 cm and a height of 4 cm, and the cut treated sheet was placed on top. Then, after placing a cover on top, it was left in a constant temperature chamber at 25 ° C with illumination. The number of surviving insects was counted for 12 to 15 days after treatment and the protection value was obtained in the same manner as in test example 2 above. The protection value was obtained in relation to the above compounds No. 11, 12, 16, 22, 38, and 39 whereby the compounds had high control effects with a protection value of at least 90%. 35

TEST EXAMPLE 7

Test on the control of effects against ladybug (Epilachna vigintioctopunctata)

[0081] An eggplant leaf segment was immersed for approximately 10 seconds in an insecticidal solution prepared to obtain a concentration of the compound of the present invention at 25 ppm or 12.5 ppm and air dried. A wet filter paper was placed on a plastic cup having a diameter of 9 cm and a height of 4 cm and the dried eggplant leaf segment was placed on top. Five larvae were released on first-second instars of ladybugs on top and after placing a cover it was left in a constant temperature chamber at 25 ° C with lighting. The dead insects were counted for 4 to 6 days after releasing them and the death rate was obtained in the same manner as that of the previous test example 1. At this point, dying insects were counted as dead insects. The death rate at 25 ppm was obtained in relation to the compounds mentioned No. 9 and 11, whereby all the compounds had high control effects with a mortality of at least 90%; and the mortality rate at 12.5 ppm was obtained in relation to the compounds mentioned No. 3, 16, 22, 38 and 39, whereby the compounds had high control effects with a mortality rate of at least 90 %.

TEST EXAMPLE 8

Test on the effects of control against fly (Musca domestica)

[0082] 10 g of culture medium were placed in a plastic cup having a diameter of 6 cm and a height of 3 cm and then 10 ml of an insecticidal solution prepared to obtain a concentration of the compound of the present were added. invention of 200 ppm, and mixed. 20 to 30 larvae of 4 days of life were released, and 5 after placing a cover on top, it was left in a constant temperature chamber at 25 ° C with illumination for 15 to 16 days. Next, the number of adults was counted and the percentage of emergency inhibition was obtained following the equation indicated below. The percentage of emergency inhibition was obtained in relation to the mentioned compounds Nº 3, 9, 11, 12 and 14 to 20, whereby the compounds had high control effects with a percentage of emergency inhibition of at least 90% 10

Emergency inhibition percentage (%) = (1- (number of adults / number of larvae released)) x100

TEST EXAMPLE 9

Test on the effects against underground termite (Coptotermes formosanus)

[0083] A filter paper was placed in a glass petri dish having a diameter of 9 cm, and 1 ml of insecticidal solution prepared to obtain a concentration of the compound of the present invention of 500 ppm. Next, 10 workers and an underground termite soldier were released and after placing a cover, they were left in a constant temperature chamber at 25 ° C with lighting.

 The number of dead workers was counted 6 days after treatment and the death rate was obtained through the equation shown below. Mortality was obtained in relation to the previous compounds Nº 3, 9, 11, 12, 14 to 16 and 22, whereby the compounds had high control effects with a mortality rate of at least 90%.

Mortality (%) = (number of dead workers / 10) x 100

TEST EXAMPLE 10

Test of systemic effects against the gray tobacco worm (Spodoptera litura)

[0084] 10 ml of an insecticidal solution prepared to obtain a concentration of the compound of the present invention of 800 ppm and 200 ppm was applied at the foot of a pumpkin at the stage of the 5th to 6th leaf planted in a pot. A wet filter paper was placed on a petri dish that had a diameter of 9 cm, and a segment of the cut pumpkin leaf was placed on top ten days after the treatment. Larvae were released in the second-third instar of gray tobacco worm and after placing a cover it was left in a constant temperature chamber at 25 ° C with illumination. The dead larvae were counted for 4 to 5 days after releasing them 30 and the mortality rate was obtained in the same manner as that of the previous test example 1. At this point, it was counted as dead insects, the dying insects. The death rate at 800 ppm was obtained in relation to the aforementioned compound No. 8, whereby it presented high control effects with a mortality rate of at least 90% and the death rate at 200 ppm was obtained in in relation to the above mentioned compounds Nº 3, 9, 11, 16, 18 and 22, whereby all the compounds had high control effects with a mortality of at least 90%.

EXAMPLE OF TEST 11

Essay on control against Hemaphysalis longicornis

[0085] It was applied on the inner surface of a petri dish having a diameter of 9 cm, 1 ml of acetone solution of a sample compound (concentration: 10 µg / ml), dropwise with a micropipette. On the other hand, as a control section, 1 ml of acetone was applied dropwise in the same way. The inner surface of the petri dish was dried and then approximately 100 larval ticks were placed and the petri dish was covered with a polyethylene sheet and sealed with an elastic band. Then, with the exception of the observation time, the petri dish was allowed to stand at a constant temperature of 25 ° C under a relative humidity of 100% and in conditions of constant darkness. The observation was carried out each time the larval ticks 45 were placed on the petri dish (after 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 45 minutes, 1 hour, 2 hours, 4 hours, 6 hours and 24 hours). The number of ticks killed after contact with the insecticidal compound was recorded. This operation was repeated twice.

[0086] The abatement index was corrected at each observation time with the Abbott correction formula indicated below. Next, a probit-time line was drawn and the average abatement time 50 (KT50 value) was obtained. In relation to the KT50 values of the corresponding sample compounds, it was 9 minutes and 8 minutes with the previous compound No. 3 and 7.5 minutes and 6 minutes with the previous compound No. 9, while it was 80 minutes and 40 minutes with the following comparative compound A and 120 minutes and 80 minutes with the following comparative compound B.

Corrected abatement index (%) = [(non-depletion index in the control section - non-depletion index in the treated section) / non-depletion index in the control section] x 100

[0087] Comparative compound A is the following compound which is compound 484 in WO 3/24222, compound 497 in WO 03/15518 and compound 2 in WO 03/15519.

Comparative compound A 5

 Comparative compound A

[0088] Comparative compound B is the compound represented below 509 in WO 03/24222, compound 530 in WO 03/15518 and compound 27 in WO 03/15519.

Comparative Compound B

 Comparative compound B 10

TEST EXAMPLE 12

Test on control effects against feline flea (Ctenocephalides felis)

[0089] 0.5 ml of an acetone solution of the compound of the present invention prepared to be 5.3 ppm was immersed in a glass tube having the flat bottom (inner diameter: 2.6 cm, bottom area: 5.3 cm2, height 12 cm). Acetone was evaporated at room temperature to obtain a dry film containing the compound of the present invention formed on the bottom surface. Ten feline flea adults (adults who had not yet sucked blood within five days after the adult's emergence) were released and exposed to the compound of the present invention. The test was carried out continuously three times.

[0090] The dead fleas was counted 48 hours after exposure and the death rate was obtained in the same manner as in the example of test 1 above. The mortality rate was obtained in relation to the previous compound No. 16, by virtue of which high control effects were demonstrated with a mortality of at least 90%.

FORMULATION EXAMPLE 1

[0091]

(1) Compound of the present invention 20 parts by weight 25

(2) Clay 72 parts by weight

(3) Lignin sodium sulfonate 8 parts by weight

[0092] The indicated compounds are uniformly mixed to obtain a wettable powder.

FORMULATION EXAMPLE 2

[0093] 30

(1) Compound of the present invention 5 parts by weight

(2) Talc 95 parts by weight

[0094] The indicated components are uniformly mixed to obtain a fine powder.

FORMULATION EXAMPLE 3

[0095]

(1) Compound of the present invention 20 parts by weight 5

(2) N, N’-dimethylacetamide 20 parts by weight

(3) Polyoxyethylene alkylphenyl ether 10 parts by weight

(4) Xylene 50 parts by weight

[0096] The indicated components are mixed uniformly and dissolved to obtain an emulsifiable concentrate. 10

FORMULATION EXAMPLE 4

[0097]

(1) Clay 68 parts by weight

(2) Lignin sodium sulfonate 2 parts by weight

(3) Polyoxyethylene alkylaryl sulfate 5 parts by weight 15

(4) Fine silica powder 25 parts by weight

[0098] A mixture of the indicated components is combined with the compound of the present invention in a 4: 1 weight ratio to obtain a wettable powder.

FORMULATION EXAMPLE 5

[0099] 20

(1) Compound of the present invention 50 parts by weight

(2) Oxylated polyalkylphenyl phosphate -

    triethanolamine 2 parts by weight

(3) Silicone 0.2 parts by weight

(4) Water 47.8 parts by weight 25

[0100] The indicated components are mixed uniformly and sprayed to obtain a base liquid and added

(5) Sodium polycarboxylate 5 parts by weight

(6) Anhydrous sodium sulfate 42.8 parts by weight

and the mixture is uniformly combined, granulated and dried to obtain a water dispersible granulate. 30

FORMULATION EXAMPLE 6

[0101]

(1) Compound of the present invention 5 parts by weight

(2) polyoxyethylenectylphenyl ether 1 part by weight

(3) polyoxyethylene phosphoric acid ester 0.1 parts / weight 35

(4) Granular calcium carbonate 93.9 parts / weight

[0102] The components (1) to (3) indicated uniformly are mixed preliminary and diluted with an appropriate amount of acetone and then the mixture is sprayed on the component (4), and the acetone is separated to Get a granulate.

FORMULATION EXAMPLE 7

[0103]

(1) Compound of the present invention 2.5 parts by weight

(2) N-methyl-2-pyrrolidone 2.5 parts by weight

(3) Soybean oil 95.0 parts by weight

[0104] The indicated components are uniformly mixed and dissolved to obtain an ultra low volume 5 formulation.

FORMULATION EXAMPLE 8

[0105]

(1) Compound of the present invention 40 parts by weight

(2) Oxylated polyalkylphenyl phosphate - 10

triethanolamine 2 parts by weight

(3) Silicone 0.2 parts by weight

(4) Xanthan rubber 0.1 parts by weight

(5) Ethylene glycol 5 parts by weight

(6) Water 52.7 parts by weight 15

[0106] The indicated components are mixed uniformly and sprayed to obtain an aqueous-based suspension concentrate.

FORMULATION EXAMPLE 9

[0107]

(1) Compound of the present invention 10 parts by weight 20

(2) Diethylene glycol monoethyl ether 90 parts by weight

[0108] The indicated components are mixed uniformly to obtain a soluble concentrate.

Claims (7)

 1. N- [2-Bromo-4-chloro-6 - [[-methyl- (cyclopropylmethyl) amino] carbonyl] phenyl] -3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole -5-carboxamide or its salt or the N-oxide thereof.  2. A process to produce N- [2-bromo-4-chloro-6 - [[-methyl- (cyclopropylmethyl) amino] carbonyl] phenyl] -3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazol-5-carboxamide or its salt, which comprises:  (1) the reaction of N- [-methyl- (cyclopropylmethyl) 2-amino-3-bromo-5-chloro benzamide chloride with 5 3-bromo 1- (3-chloro-pyridin-2-yl) chloride -1H-5-pyrazole-carbonyl, or  (2) the reaction of 2- [3-bromo-1 (3-chloro-2-pyridyl) -1H-pyrazol-5-yl] -6-chloro-8-bromo-4H-3,1-benzoxazine-4 -one with a -methyl-cyclopropylmethylamine hydrochloride.  3. A pesticide containing the anthranilamide compound or its salt or an N-oxide thereof, as defined in claim 1, as an active ingredient. 10  4. A pesticide according to claim 3  (i) for use as a pesticide in agriculture or horticulture.  (ii) for use as an insecticide, acaricide or nematocide,  (iii) for use as a pesticide against parasites in animals, or  (iv) for use as a pesticide against external parasites in animals. fifteen  5. A preventive or therapeutic agent for an animal disease caused by a parasite containing the anthranilamide compound or a salt or N-oxide thereof as defined in claim 1, as an active ingredient.  6. A method of controlling a pest comprising the application of an effective amount of the anthranilamide compound or a salt or N-oxide thereof, as defined in claim 1, except for a method 20 for the treatment of an organism Human or animal through therapy.