CN101508692B - Anthranilamides, process for the production thereof, and pest controllers containing the same - Google Patents

Abstract

The invention provides a novel anthranilamide compound or its salt which is useful as a pesticide; a process for its production; and a pesticide containing such a compound as an active ingredient. An anthranilamide compound represented by the formula (I) or its salt. In the formula, R<1> is halogen, alkyl, haloalkyl, etc.; each of R<2> and R<3> which are independent of each other, is halogen, alkyl, haloalkyl, etc.; A is alkyl substituted by Y; Y is C 3-4 cycloalkyl which may be substituted by at least one substituent selected from the group consisting of halogen, alkyl and haloalkyl; m is from 0 to 4; n is0 or 1; and q is from 0 to 4.

Description

Anthranilamides, its manufacture method and contain the noxious organism control agent of this compounds

The application is to be on February 16th, 2005 applying date, and application number is 200580004523.2, and denomination of invention is divided an application for the Chinese patent application of " anthranilamides, its manufacture method and contain the noxious organism control agent of this compounds ".

Technical field

Patent documentation 1, patent documentation 2, patent documentation 3 and patent documentation 4 disclose respectively the anthranilamides with specific chemical structure.But, in these patent documentations, all do not have record to have a compound that is equivalent to the A in the aftermentioned formula of the present invention (I), this A as substituting group by the alkyl of C3-4 cycloalkyl substituted.

In addition, patent documentation 5 discloses 4 anthranilamides with cyano group of phenyl ring.But, the R in formula of the present invention described later (I) ¹Definition in do not comprise cyano group, both chemical structure is different.

Patent documentation 1: international open communique WO03/24222 number

Patent documentation 2: international open communique WO03/15518 number

Patent documentation 3: international open communique WO03/15519 number

Patent documentation 4: international open communique WO01/70671 number

Patent documentation 5: international open communique WO04/67528 number

Summary of the invention

For many years, although used a lot of noxious organism control agents, many agent for preventing and eliminating exist that effect is insufficient, its use such as is restricted at the variety of issue behind the harmful organism acquired resistance.

The present invention wishes to develop the few new noxious organism control agent of such shortcoming, for example, can prevent and kill off the various harmful organisms that become problem in the agriculture and garden field or the noxious organism control agent that parasitizes the harmful organism of animal.

The inventor has carried out various researchs in order to find more excellent noxious organism control agent to anthranilamides.It found that new anthranilamides or its salt have high preventive effect for harmful organism under low dose, thereby have finished the present invention.

That is, the present invention relates to anthranilamides or its salt, its manufacture method of formula (I) expression and contain their noxious organism control agent etc.,

[changing 1]

(in the formula, R ¹For halogen, alkyl, haloalkyl, alkenyl, halogenated alkenyl, alkynyl, halo alkynyl, alkoxyl group, halogenated alkoxy, alkyl-carbonyl, halogenated alkyl carbonyl, alkoxy carbonyl, halo alkoxy carbonyl, can substituted phenyloxycarbonyl, nitro or formyl radical; R ²And R ³Independent respectively is halogen, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy or cyano group; The alkyl of A for being replaced by Y; The C3-4 cycloalkyl that Y replaces for 1 substituting group in the group that can be selected from halogen, alkyl and haloalkyl composition at least; M is 0～4; N is 0 or 1; Q is 0～4, and condition is R ¹Be fluorine atom, chlorine atom, bromine atoms or methyl and other the R in 2 replacements of phenyl ring ¹During for the halogen of 4 replacements of phenyl ring, this halogen of 4 is fluorine atom or chlorine atom).

With the new anthranilamides of above-mentioned formula (I) noxious organism control agent as effective constituent, under low dose, have for the high preventive effect of harmful organism.

Embodiment

As R ¹In can substituted phenyloxycarbonyl substituting group; for example can list halogen, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, alkylthio, halogenated alkylthio, alkyl sulphinyl, haloalkyl sulfinyl, alkyl sulphonyl, halogenated alkyl sulfonyl, cyano group, nitro etc.Substituent replacement number like this can be for more than 1 or 2, and in the occasion more than 2, each substituting group can be identical or different.In addition, each substituent the position of substitution can be in arbitrary position.

The replacement number of substituting group Y among the A can be for more than 1 or 2, and in the occasion more than 2, each substituting group Y can be identical or different.In addition, the position of substitution of substituting group Y can be arbitrary position.The replacement number of substituting group Y among the A is preferably 1.

As the replacement number of substituent halogen, alkyl or the haloalkyl of the C3-4 cycloalkyl among the Y, can be for more than 1 or 2, in the occasion more than 2, each substituting group can be identical or different.In addition, each substituent the position of substitution can be arbitrary position.C3-4 cycloalkyl among the Y is preferably without replacement, or has above-mentioned substituent occasion, and it replaces number and is preferably 1～5.

As R ¹, R ², R ³Or the halogen among the Y or as substituent halogen, can list each atom of fluorine, chlorine, bromine or iodine.Number as substituent halogen can be for more than 1 or 2, and in the occasion more than 2, each halogen can be identical or different.In addition, the position of substitution of halogen can be arbitrary position.

R ¹, R ², R ³, alkyl or moieties among A or the Y, can be any of straight or branched.As its concrete example, can list alkyl of the C1-6 that methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, amyl group, hexyl are such etc.

R ¹In alkenyl or alkenyl part, can be any of straight or branched.As its concrete example, can list alkenyl of the C2-6 that vinyl, 1-propenyl, allyl group, pseudoallyl, 1-butylene base, 1,3-butadiene base, 1-hexenyl are such etc.

R ¹In alkynyl or alkynyl part, can be any of straight or branched.As its concrete example, can list alkynyl of the such C2-6 of ethynyl, 2-butyne base, valerylene base, 3-hexin base etc.

As the C3-4 cycloalkyl among the Y or the concrete example of cycloalkyl moiety, can list cyclopropyl or cyclobutyl, wherein preferred cyclopropyl.

Salt as the anthranilamides of above-mentioned formula (I) comprises all salt that is allowed on the agricultural.For example can list sodium salt, the such an alkali metal salt of sylvite; Magnesium salts, the such alkali earth metal salt of calcium salt; Diformazan ammonium salt, the such ammonium salt of triethylammonium salts; Hydrochloride, perchlorate, vitriol, the such inorganic acid salt of nitrate; Organic acid salt that acetate, mesylate are such etc.

In the anthranilamides of above-mentioned formula (I), sometimes have optical isomer, the such isomer of geometrical isomer, the present invention comprise each isomer and isomer mixture the two.In addition, in the scope of the technology general knowledge of this technical field, the present invention also comprises the various isomer beyond above-mentioned.In addition, although sometimes cause forming the situation of the chemical structure different from above-mentioned formula (I) because of the kind of isomer, be the relation that has isomer so long as those skilled in the art just can fully realize this, clearly be within the scope of the invention therefore.

The anthranilamides of above-mentioned formula (I) or its salt (being designated hereinafter simply as the compounds of this invention) can be made according to the manufacture method of following reaction [A]～[B] and common salt.

[changing 2]

R ¹, R ², R ³, A, m, n and q as mentioned above, Z be the chlorine atom ,-OH or C _1-4Alkoxyl group.

Z is the occasion of chlorine atom, and reaction [A] can be carried out in the presence of alkali usually.

As alkali, can for example suitably select sodium hydroxide, the such alkali metal hydroxide of potassium hydroxide; Yellow soda ash, the such alkaline carbonate of salt of wormwood; Sodium hydride, the such alkalimetal hydride of potassium hydride KH; Trimethylamine 99, triethylamine, tri-isopropyl amine, diisopropylethylamine, pyridine, DMAP, 2,6-lutidine, 4-tetramethyleneimine pyridine, N-methylmorpholine, N, accelerine, N, N-Diethyl Aniline, N-ethyl-methylphenylamine, 1, one kind or two or more in tertiary amines that 8-diazabicyclo [5.4.0]-7-hendecene, Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane are such etc.Can use alkali with 1～5 times of mole, preferred 1～2.5 times of mole with respect to the compound of formula (II).

Z is the occasion of chlorine atom, and reaction [A] can be carried out in the presence of solvent as required.As solvent, so long as for the solvent of reactionlessness, any can.For example can suitably select ether, butyl ethyl ether, tetrahydrofuran (THF), diox, the such ethers of glycol dimethyl ether; Chlorobenzene, dichlorobenzene, methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride, trichloroethane, the such halogenated hydrocarbon of Ethylene Dichloride; Such aromatic hydrocarbon based of benzene,toluene,xylene; Acetonitrile, propionitrile, DMF, methyl-sulphoxide, hexamethylphosphoramide, tetramethylene sulfone, N,N-DIMETHYLACETAMIDE, the such polar aprotic solvent of N-Methyl pyrrolidone; Methyl acetate, ethyl acetate, the such ester class of propyl acetate; One kind or two or more in ketone that acetone, metacetone, methyl ethyl ketone, mibk are such etc.

Z is the occasion of chlorine atom, and reaction [A] is carried out under-20～+ 60 ℃ usually, preferably carries out under 0～30 ℃.Its reaction times was generally about 1～24 hour, was preferably about 2～12 hours.

Z is-occasion of OH, and reaction [A] can be carried out in the presence of dehydrating condensation agent and solvent usually.

As dehydrating condensation agent, can list N, N '-dicyclohexylcarbodiimide, 1,3-DIC, the such carbodiimide class of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride; In addition, can list, 1,1 '-carbonyl-two-1H-imidazoles, dichloro-phenyl phosphate, diethyl phosphorocyanidate, 1,3,5-three azepines-2,4,6-triphosphine-2,2,4,4,6,6-chlordene, cyanuryl chloride, isobutyl chlorocarbonate, chlorosulfonic acid isocyanate, trifluoroacetic anhydride etc.

As solvent, so long as for the solvent of reactionlessness any can.For example can suitably select ether, butyl ethyl ether, tetrahydrofuran (THF), diox, the such ethers of glycol dimethyl ether; Chlorobenzene, dichlorobenzene, methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride, trichloroethane, the such halogenated hydrocarbon of Ethylene Dichloride; Such aromatic hydrocarbon based of benzene,toluene,xylene; Acetonitrile, propionitrile, DMF, methyl-sulphoxide, hexamethylphosphoramide, tetramethylene sulfone, N,N-DIMETHYLACETAMIDE, the such polar aprotic solvent of N-Methyl pyrrolidone; Methyl acetate, ethyl acetate, the such ester class of propyl acetate; Acetone, metacetone, methyl ethyl ketone, the such ketone of mibk; One kind or two or more in aliphatic hydrocarbon that pentane, hexane, heptane, octane, hexanaphthene are such etc.

Z is-occasion of OH, and reaction [A] can be carried out under-20～+ 60 ℃ usually, preferably carries out under 0～30 ℃.Its reaction times was generally about 0.5～24 hour, was preferably about 1～12 hour.

Z is C _1-4The occasion of alkoxyl group, reaction [A] can be carried out in the presence of alkali and solvent usually.

As alkali, for example can suitably select sodium hydride, the such alkalimetal hydride of potassium hydride KH; Sodium methylate, sodium ethylate, the such alkali metal alcoholates of sodium tert-butoxide; Trimethylamine 99, triethylamine, tri-isopropyl amine, diisopropylethylamine, pyridine, DMAP, 2,6-lutidine, 4-tetramethyleneimine pyridine, N-methylmorpholine, N, accelerine, N, N-Diethyl Aniline, N-ethyl-methylphenylamine, 1, one kind or two or more in tertiary amines that 8-diazabicyclo [5.4.0]-7-hendecene, Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane are such etc.Can use alkali with 1～5 times of mole, preferred 1～2.5 times of mole with respect to the compound of formula (II).

As solvent, so long as for the solvent of reactionlessness any can.For example can suitably select ether, butyl ethyl ether, tetrahydrofuran (THF), diox, the such ethers of glycol dimethyl ether; Such aromatic hydrocarbon based of benzene,toluene,xylene; Acetonitrile, propionitrile, DMF, methyl-sulphoxide, hexamethylphosphoramide, tetramethylene sulfone, N,N-DIMETHYLACETAMIDE, the such polar aprotic solvent of N-Methyl pyrrolidone; One kind or two or more in alcohols that methyl alcohol, ethanol, propyl alcohol, propyl carbinol, the trimethyl carbinol are such etc.

Z is C _1-4The occasion of alkoxyl group, reaction [A] can be carried out under 0～120 ℃ usually, preferably carries out under 20～80 ℃.Its reaction times was generally about 0.5～24 hour, was preferably about 1～12 hour.

The compound of above-mentioned formula (II) or formula (III) is respectively known compound, or can be according to known data preparation.For example, the compound of formula (II) can be according to Synthesis,, the preparation of the method for 505 pages of records in 1980.The compound of formula (III) can be according to the method preparation of scheme 9～22 records among the WO03/24222.

[changing 3]

R ¹, R ², R ³, A, m, n and q as mentioned above.

Reaction [B] can be carried out in the presence of solvent usually.

As solvent, so long as for the solvent of reactionlessness any can.For example can suitably select ether, butyl ethyl ether, tetrahydrofuran (THF), diox, the such ethers of glycol dimethyl ether; Chlorobenzene, dichlorobenzene, methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride, trichloroethane, the such halogenated hydrocarbon of Ethylene Dichloride; Such aromatic hydrocarbon based of benzene,toluene,xylene; One kind or two or more in polar aprotic solvent that acetonitrile, propionitrile, DMF, methyl-sulphoxide, hexamethylphosphoramide, tetramethylene sulfone, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone are such etc.

Reaction [B] can be carried out under 0～120 ℃ usually, preferably carries out under 20～80 ℃.Its reaction times can be about 0.5～24 hour usually, is preferably about 1～12 hour.

The compound of above-mentioned formula (IV) is known compound, or can be prepared according to known data.For example, the compound of formula (IV) can be according to Org.Prep.Proceed.Int.,, the method for the method of 25 volumes, 585 pages of records, 8～10 records of the scheme among the WO03/24222 in 1993 or according to the method preparation of their developments.

Comprise novel compound in above-mentioned formula (V) compound.This compound can be standby according to the Gabriel legal system, for example can be prepared according to following reaction [C].

[changing 4]

In reaction [C], A is for as mentioned above, T be halogen ,-OSO ₂G (G is the sulphonate residue) or-OH.T be halogen or-OSO ₂During G, M is sodium or potassium, and T is-and during OH, M is hydrogen atom.As above-mentioned sulphonate residue, can list methyl, the such C of ethyl _1-6Alkyl; Can be by C _1-6The phenyl that replaces of alkyl etc.

T be halogen or-OSO ₂G and M are the occasion of sodium or potassium, and the 1st operation of reaction [C] can be carried out in the presence of solvent usually.

As solvent, so long as for the solvent of reactionlessness any can.For example can suitably select ether, butyl ethyl ether, tetrahydrofuran (THF), diox, the such ethers of glycol dimethyl ether; Such aromatic hydrocarbon based of benzene,toluene,xylene; Acetonitrile, propionitrile, DMF, methyl-sulphoxide, hexamethylphosphoramide, tetramethylene sulfone, N,N-DIMETHYLACETAMIDE, the such polar aprotic solvent of N-Methyl pyrrolidone; One kind or two or more in alcohols that methyl alcohol, ethanol, propyl alcohol, propyl carbinol, the trimethyl carbinol are such etc.

T be halogen or-OSO ₂G and M are the occasion of sodium or potassium, and the 1st operation of reaction [C] can be carried out under 0～150 ℃ usually, preferably carries out under 30～110 ℃.Its reaction times can be about 0.5～24 hour usually, is preferably about 1～12 hour.

Be the occasion of hydrogen atom at T for-OH and M, the 1st operation of reaction [C] is carried out according to the light method of prolonging usually.For example, can in the presence of solvent, carry out with azodicarboxy acid dialkyl ester and triphenylphosphine.Above-mentioned azodicarboxy acid dialkyl ester and triphenylphosphine usually are respectively equimolar degree with the compound with respect to formula (VI) and use.As above-mentioned azodicarboxy acid dialkyl ester, for example can list diethylazodicarboxylate, diisopropyl azo-2-carboxylic acid etc.

As solvent, so long as for the solvent of reactionlessness any can.For example can suitably select ether, butyl ethyl ether, tetrahydrofuran (THF), diox, the such ethers of glycol dimethyl ether; Chlorobenzene, dichlorobenzene, methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride, trichloroethane, the such halogenated hydrocarbon of Ethylene Dichloride; One kind or two or more in the such aromatic hydrocarbon based grade of benzene,toluene,xylene.

Be the occasion of hydrogen atom at T for-OH and M, the 1st operation of reaction [C] can be carried out under 0～80 ℃ usually, preferably carries out under 20～60 ℃.Its reaction times can be about 0.5～24 hour usually, is preferably about 1～16 hour.

The 2nd operation of reaction [C] can in the presence of solvent, be undertaken by the compound that comes breakdown (VIII) with hydrazine usually.Above-mentioned hydrazine can use in equimolar degree with respect to formula (VIII) compound usually.

As solvent, so long as for the solvent of reactionlessness any can.For example can suitably select ether, butyl ethyl ether, tetrahydrofuran (THF), diox, the such ethers of glycol dimethyl ether; Such aromatic hydrocarbon based of benzene,toluene,xylene; One kind or two or more in alcohols that methyl alcohol, ethanol, propyl alcohol, propyl carbinol, the trimethyl carbinol are such etc.

The 2nd operation of reaction [C] can be carried out under 0～140 ℃ usually, preferably carries out under 30～100 ℃.Its reaction times can be about 0.5～24 hour usually, is preferably about 2～12 hours.

The preferred configuration of noxious organism control agent that contains the compounds of this invention is as described below.The noxious organism control agent that contains the compounds of this invention, as the agent for preventing and eliminating that for example in the agriculture and garden field, becomes the various harmful organisms of problem, be the agriculture and garden noxious organism control agent, or parasitize the harmful organism of animal agent for preventing and eliminating, be that animal Parasites agent for preventing and eliminating is particularly useful.

As the agriculture and garden noxious organism control agent, for example, as desinsection, to kill mite, nematicide, kill the soil pests agent be useful, specifically, for the phytotrophy mite class of preventing and kill off Tetranychus urticae, tetranychus telarius, kamisawa tetranychus, citrus red mite (crm), panonychus ulmi, Polyphagotarsonemus latus Banks, tangerine peronium goitre mite, water arum root mite etc.; Diamond-back moth, lopper worm, prodenia litura, carpocapsa pononella, bollworm, tobacco budworm, cigarette poison moth, cnaphalocrocis medinalls guenee, adoxophyes moth, codling moth, the little food heart of peach moth, oriental fruit months, black cutworm, yellow cutworm, colorado potato beetles, aulacophora femoralis, Mexico's cotton boll resemble, the Agricultural pests class of Phytophthira, plant hopper, Amrasca biguttula (Ishida) class, shell insects, stinkbug class, aleyrodid class, thrips class, locustamigratoria, flowerfly class, cockchafer subclass, ant class, liriomyza bryoniae class etc.; The plant parasitic nematodes class of root knot nematode class, golden nematode class, root spot threadworms, Aphelenchoides oryzae Yokoo, strawberry bud nematode, pine wood nematodes etc.; The snails of slug, strong snail etc.; Pillworm, damp worm etc. etc. the such soil pests class of sufficient class; The sanitary insect pest class of Pasteur fowl thorn mite, housefly, culex, cockroach class etc.; Gelechiid, Callosobruchus chinensis, red flour beetle, the first-class grain depot pest type of bloom; Bag casemaking clothes moth, carpet are justified such clothing, house pest types such as skin is stupid, Coptotermes formosanus Shtrari．; Preventing and kill off effectively of the indoor dust mite class that tyrophagus putrescentiae, dust mite, southern pawl mite etc. are such etc.Wherein, contain the agriculture and garden noxious organism control agent of the compounds of this invention, phytotrophy mite class, Agricultural pests class, plant parasitic nematodes class etc. are effective especially for preventing and kill off.In addition, contain the agriculture and garden noxious organism control agent of the compounds of this invention, also effective for the various resistivity insects of preventing and kill off the medicament of organic phosphate agent, carbamate agent, pyrethroid agent etc.And then, the compounds of this invention is because have the excellent transitivity that soaks into, so by processing soil with the agriculture and garden that contains the compounds of this invention with noxious organism control agent, prevent and kill off soil harmful insect class, mite class, threadworms, snails, etc. also can prevent and kill off the pest type of leaves and stems in the sufficient class.

As other preferred configuration of the noxious organism control agent that contains the compounds of this invention, can list Comprehensive Preventing except the agriculture and garden noxious organism control agent of above-mentioned phytotrophy mite class, Agricultural pests class, plant parasitic nematodes class, snails, soil pests class etc.

The agriculture and garden noxious organism control agent that contains the compounds of this invention; usually mix the auxiliary on this compound and the various agricultural chemicals; the preparation that forms the various forms of pulvis, granule, particle wettable powder, wettable powder, aqueous suspension agent, oiliness suspension agent, water solvent, emulsion, liquor, paste, aerosol, micro-spraying agent etc. uses; but as long as be fit to purpose of the present invention, then can make all preparation forms of usually in this field, using.As the auxiliary that uses in the preparation, can list the solid carrier of the mixture, clay, yellow soda ash, sodium bicarbonate, saltcake, zeolite, starch etc. of diatomite, slaked lime, calcium carbonate, talcum, white carbon(ink), kaolin, wilkinite, kaolinite and sericite; The solvent of water, toluene, dimethylbenzene, solvent naphtha, diox, acetone, isophorone, methyl iso-butyl ketone (MIBK), chlorobenzene, hexanaphthene, methyl-sulphoxide, DMF, N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, alcohol etc.; Soap, benzoate, alkyl sulfo succinate, dialkyl sulfosuccinates, polycarboxylate, alkyl sulfuric ester salt, alkyl-sulphate, alkyl aryl sulfate, alkyl biphenyl sulphate, the alcohol sulfuric acid, alkylsulfonate, alkylaryl sulphonate, arylsulphonate, ligninsulfonate, alkyl diphenyl base ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, poly styrene sulfonate, alkyl phosphate salt, alkylaryl phosphoric acid salt, the styryl aryl orthophosphate, the Voranol EP 2001 sulfuric acid, polyoxyethylene alkylaryl ether vitriol, the polyoxyethylene alkylaryl ether sulfuric acid, Voranol EP 2001 phosphoric acid salt, polyxyethylated aryl phosphate ester salt, the tensio-active agent of the anionic species that the salt of naphthalene sulfonic acidformaldehyde condensation product is such or developping agent; Sorbitan fatty acid esters, glycerol fatty acid ester, fatty acid polyglycerol ester, the fatty acid alcohol polyglycol ether, acetylenediol, acetylene alcohol, the oxyalkylene block polymer, Voranol EP 2001, polyoxyethylene alkylaryl ether, polyoxyethylene styryl aryl ethers, polyoxyethylene glycol alkyl ether, polyoxyethylene glycol, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid esters, the polyoxyethylene glycerol fatty acid ester, polyoxyethylene hardened castor oil, the tensio-active agent of the nonionic class that the polyoxypropylene fatty acid ester is such, developping agent; Vegetables oil or the mineral wet goods of sweet oil, melon baobab oil, Viscotrol C, plam oil, Camellia oil, Oleum Cocois, sesame oil, Semen Maydis oil, Rice pollard oil, Peanut oil, Oleum Gossypii semen, soybean oil, rapeseed oil, Toenol 1140, tung oil, whiteruss etc.The various compositions of these auxiliarys only otherwise break away from purpose of the present invention, can suitably be selected one kind or two or more the use.In addition, also can be outside above-mentioned auxiliary from the known material in this field suitable choice for use.Also can use normally used various auxiliarys such as extender, thickening material, anti-sedimentation agent, frostproofer, dispersion stabilizer, poisoning light-weight additive, mould inhibitor.The mixing ratio of the compounds of this invention and various auxiliarys is 0.001: 99.999～95: 5, is preferably 0.005: 99.995～90: 10.Such preparation can directly use when reality is used, and after thinner that also can water etc. is diluted to normality, adds as required various developping agents (tensio-active agent, vegetables oil, mineral wet goods) and uses.

Agriculture and garden the using with noxious organism control agent of containing the compounds of this invention, according to meteorological conditions, preparation form, use period, use the place, the difference of the kind of disease and insect or situation occurred etc. and difference, can not decide without exception, but generally with 0.05～800000ppm, the effective constituent concentration that is preferably 0.5～500000ppm is used, the amount of application of its per unit area is that per 1 hectare of the compounds of this invention is 0.05～50000g, is preferably 1～30000g.In addition,, can carry out according to using of above-mentioned noxious organism control agent with the using of noxious organism control agent as other the agriculture and garden of preferred configuration of the noxious organism control agent that contains the compounds of this invention.The present invention also comprises the method for control of the harmful organism that utilizes such application process, particularly the method for control of phytotrophy mite class, Agricultural pests class, plant parasitic nematodes class.

The agriculture and garden that contains the compounds of this invention is with the various preparations of noxious organism control agent or using of its dilution, usually can utilize the application process of generally carrying out namely to scatter (such as scatter, spray, spray (misting), atomizing (atomizing), spread grain, used for ponds method etc.), soil application (sneak into, perfusion etc.), surface applied (coating, powder clothing, coating etc.), flood poison bait etc. and carry out.In addition, above-mentioned effective constituent is mixed to gives domestic animal in the feed, also can hinder generation and the fertility of insect, particularly harmful insect in its movement.Can utilize in addition so-called ultrahigh concentration to scatter on a small quantity method (ultra low volume) uses.In the method, can contain 100% activeconstituents.

In addition, the agriculture and garden that contains the compounds of this invention can be used with or share with other agricultural chemicals, fertilizer, poisoning light-weight additive etc. with noxious organism control agent, and such occasion shows more excellent effect, functionality.As other agricultural chemicals, can list weedicide, sterilant, miticide, nematocides, kill soil pests agent, sterilant, antiviral agent, attractive substance, microbiotic, plant hormone, plant-growth regulator etc.Particularly used or share the one kind or two or more mixing Pesticidal composition of the effective constituent compound of the compounds of this invention and other agricultural chemicals with, can be with period of the scope of application, chemicals treatment, prevent and kill off the direction improvement of becoming better such as active.In addition, the effective constituent compound of the compounds of this invention and other agricultural chemicals can mix the preparation of making respectively and use when scattering, also both can be made together preparation and use.The present invention also comprises such mixing Pesticidal composition.

The ratio of mixture of the effective constituent compound of the compounds of this invention and other agricultural chemicals, according to meteorological conditions, preparation form, use period, use the place, the difference of the kind of disease and insect or situation occurred etc. and difference, can not decide without exception, but be generally 1: 300～300: 1, be preferably 1: 100～100: 1.In addition, using suitable amount and be as per 1 hectare total effective constituent compound amount is 0.1～50000g, is preferably 1～30000g.The present invention comprises the method for control of the harmful organism of the application process of utilizing such mixing Pesticidal composition.

As the sterilant in above-mentioned other the agricultural chemicals, miticide, nematocides or kill soil pests agent, i.e. the effective constituent compound (popular name of insect pest control agent; Comprise in the application), can list for example Profenofos (Profenofos), SD-1750 (Dichlorvos), fenamiphos (Fenamiphos), Sumithion (Fenitrothion), EPN (EPN), diazinon (Diazinon), methyl chloride pyrrole phosphorus (Chlorpyrifos-methyl), acephate (Acephate), Toyodan (Prothiofos), lythidathion (Fosthiazate), Phosphocarb, cadusafos (Cadusafos), thiodemeton (Dislfoton), chlorine pyrazothion (Chlorpyrifos), go out and grant pine (Demeton-S-methyl), Rogor (Dimethoate), acephatemet (Methamidophos), the such organophosphorus ester compound of thiophos (Parathion);

Carbaryl (Carbaryl), Propoxur (Propoxur), aldicarb (Aldicarb), carbofuran (Carbofuran), thiodicarb (Thiodicarb), methomyl (Methomyl), oxamyl (Oxamyl), ethiofencarb (Ethiofencarb), Aphox (Pirimicarb), fenobucarb (Fenobucarb), carbosulfan (Carbosulfan), the such amino formate compounds of benfuracarb (Benfuracarb);

Cartap (Cartap), thiocyclam (Thiocyclam), the such nereistoxin analog derivative of bensultap (Bensultap);

Kelthane (Dicofol), tetradifon (Tetradifon), the such organochlorine compounds of 5a,6,9,9a-hexahydro-6,9-methano-2,4 (Endosulfan);

The such organo-metallic compounds of fenbutatin oxide (Fenbutatin Oxide);

Fenvalerate (Fenvalerate), permethrin (Permethrin), Cypermethrin (Cypermethrin), Deltamethrin (Deltamethrin), cyhalothrin (Cyhalothrin), tefluthrin (Tefluthrin), ether chrysanthemum ester (Ethofenprox), Fenvalerate (Fenpropathrin), the such pyrethroid coumpound of bifenthrin (Bifenthrin);

Diflubenzuron (Diflubenzuron), UC 62644 (Chlorfluazuron), tetrafluoro urea (Teflubenzuron), flufenoxuron (Flufenoxuron), chlorine fragrant new (Lufenuron), napropamide (Novaluron), bistrifluron (Bistrifluron), the such benzoyl urea compound of polyfluoro worm uride (Noviflumuron);

Methoprene (Methoprene), Nylar (Pyriproxyfen), the such class hebin compound of fenoxycarb (Fenoxycarb);

The such pyridazinone compound of pyridaben (Pyridaben);

Fenpyroximate (Fenpyroximate), ethiprole (Fipronil), tebufenpyrad (Tebufenpyrad), ethiprole (Ethiprole), Tolfenpyrad (Tolfenpyrad), Acetoprole, Pyrafluprole, the such pyrazole compound of Pyriprole;

The anabasine of Provado (Imidacloprid), Ti304 (Nitenpyram), acetamiprid (Acetamiprid), thiacloprid (Thiacloprid), Diacloden (Thiamethoxam), clothianadin (Clothianidin), MTI-446 (Dinotefuran) etc.;

The hydrazine class compound of worm hydrazides (Tebufenozide), methoxyfenozide (Methoxyfenozide), ring worm hydrazides (Chromafenozide), chlorine worm hydrazides (Halofenozide) etc.;

The dinitrobenzene compounds, organosulfur compound, urea compound, compound in triazine class, hydrazone compounds, or can enumerate as other compound, flonicamid (Flonicamid), Buprofezin (Buprofezin), hexythiazox (Hexythiazox), amitraz (Amitraz), chlordimeform (Chlordimeform), salifluofen (Silafluofen), triaxamate (Triazamate), pymetrozine (Pymetrozine), pyrimidifen (Pyrimidifen), Chlorfenapyr (Chlorfenapyr), indoxacarb (Indoxacarb), acequinocyl (Acequinocyl), second mite azoles (Etoxazole), cyromazine (Cyromazine), 1, the 3-dichloropropylene (1,3-dichloropropene), methamidophos (Diafenthiuron), Benclothiaz, Flufenerim, pyridalyl (Pyridalyl), spirodiclofen (Spirodiclofen), Bifenazate (Bifenazate), season ketone first mite ester (Spiromesifen), propargite (Propargite), clofentezine (Clofentezine), Fluacrypyrim (Fluacrypyrim), Flubendiamide, Cyflumetofen, Metaflumizone, the compound that Amidoflumet is such.And then, also can use, also use such microbial pesticides such as BT agent, Insect Pathogenic viral agent, rileyi agent, the former thread microbial inoculum of oxyuriasis with; Avrmectin (Avermectin), because of the spit of fland benzoate (Emamectin-Benzoate) that goes out, the close spit of fland of going out (Milbemectin), pleocidin (Spinosad), ivermectin (Ivermectin), the such microbiotic of Lepimectin; Natural goods that Kuliansu (Azadirachtin), tubatoxin (Rotenone) are such etc.

Effective constituent compound (popular name as the sterilant in above-mentioned other the agricultural chemicals; Comprise in the part application), can list for example mepanipyrim (Mepanipyrim), pyrimethanil (Pyrimethanil) and the such Pyrimethamine hcl compounds of ring the third pyrimidine (Cyprodinil);

Triazolone (Triadimefon), Bitertanol (Bitertanol), fluorine bacterium azoles (Triflumizole), etaconazole (Etaconazole), Wocosin 50TK (Propiconazole), Topaze (Penconazole), fluzilazol (Flusilazole), nitrile bacterium azoles (Myclobutanil), cyproconazole (Cyproconazole), tebuconazole (Terbuconazole), own azoles alcohol (Hexaconazole), furconazole_cis (Furconazole-cis), prochloraz (Prochloraz), metconazole (Metconazole), according to general seat (Epoxiconazole), fluorine ether azoles (Tetraconazole) Evil imidazoles (Oxpoconazole), the pyrrole compounds that Sipconazole is such;

The such quinoxaline compound of quinomethionate (Quinomethionate);

Maneb (Maneb), zineb (Zineb), zinc manganese ethylenebisdithiocarbamate (Mancozeb), polycarbamate (Polycarbamate), the such dithio amino formate compounds of propineb (Propineb);

Phthalide (Fthalide), m-tetrachlorophthalodinitrile (Chlorothalonil), the such organochlorine compounds of quintozene (Quintozene);

F-1991 (Benomyl), thiophanate methyl (Thiophanate-Methyl), derosal (Carbendazim), the such glyoxaline compound of cyazofamid (Cyazofamid);

The pyridyl amine compound that fluazinam (Fluazinam) is such;

The malonamide nitrile compounds that cymoxanil (Cymoxanil) is such;

Metaxanin (Metalaxyl), Evil frost spirit (Oxadixyl), fenfuram (Ofurace), M 9834 (Benalaxyl), furalaxyl (Furalaxyl), cyprofuram (Cyprofuram), such phenylamide compound;

The sulfenic acid compounds that dichlofluanid (Dichlofluanid) is such;

Copper hydroxide (Cupric hydroxide) and the such copper compounds of oxinecopper (Oxine Copper);

The such De isoxazole compounds of hydoxyisoxazole (Hydroxyisoxazole);

Fosetyl (Fosetyl-Al), tolclofosmethyl (Tolcofos-Methyl), S-benzyl O, O-di-isopropyl thiophosphatephosphorothioate, O-ethyl S, S-Diphenyl disulfide substituted phosphate, ethyl halide are for the such organophosphorus compound of aluminum phosphate;

Vancide 89 (Captan), Difolatan (Captafol), the such N-halo alkylthio compounds of Phaltan (Folpet);

Procymidone (Procymidone), isopropyl fixed (Iprodione) and two such carbimide compounds of vinclozolin (Vinclozolin).

Fultolanil (Flutolanil), the third oxygen mebenil (Mepronil), the such benzophenone aminated compounds of zoxamide (Zoxamid);

The such piperazine compounds of triforine (Triforine);

The such pyridine compounds and their of pyrifenox (Pyrifenox);

Fenarimol (Fenarimol), the such methyl alcohol compounds of flutriafol (Flutriafol);

The such piperidines of fenpropidin (Fenpropidine);

The such morpholine kind compound of fenpropimorph (Fenpropimorph);

Fentin hydroxide (Fentin Hydroxide), the such organic tin compound of triphenyltin acetate (FentinAcetate);

The such carbamide compounds of pencycuron (Pencycuron);

The cinnamic acid compound that dimethomorph (Dimethomorph) is such;

The phenyl carbamate compounds that the mould prestige of second (Diethofencarb) is such;

Fu Evil bacterium (Fludioxonil) and the such cyanopyrrole compounds of fenpiclonil (Fenpiclonil);

Nitrile Azoxystrobin (Azoxystrobin), kresoxim-methyl (Kresoxim-Methyl), fork phenalgin acid amides (Metominofen), oxime bacterium ester (Trifloxystrobin), ZEN 90160 (Picoxystrobin), Strobilurin (Pyraclostrobin), such imines bacterium (strobilurin) compounds;

Azolactone bacterium (Famoxadone) Zhe Yang De oxazolidinone compounds;

The such thiazole amide compound of Guardian (Ethaboxam);

The silyl amides that Silthiopham (Silthiopham) is such;

The amino acid amide amino formate compounds that zinc 1,2-propylene bisdithiocarbamate (Iprovalicarb) is such;

The such imidazolines of fenamidone (Fenamidone);

The hydroxyanilines compounds that fenhexamid (Fenhexamid) is such;

The such benzenesulfonamides of flusulfamide (Flusulfamid);

Anthraquinone analog compound; The β-crotonic acid compounds; As microbiotic or other compound, can list isoprothiolane (Isoprothiolane), tricyclazole (Tricyclazole), pyroquilon (Pyroquilon), diclomezin (Diclomezine), probenazole (Probenazole), quinoxyfen (Quinoxyfen), hundred dimension clever mono-hydrochloric salts (Propamocarb Hydrochloride), volution bacterium amine (Spiroxamine), trichloronitromethane (Chloropicrin), dazomet (Dazomet), metamsodium (Metam-sodium) etc.

In addition, as can use with the compounds of this invention or and the agricultural chemicals of usefulness, " the effective constituent compound, the particularly compound of soil treatment type etc. of the weedicide of agrochemistry handbook (Farm Chemicals Handbook version in 2002) record are for example arranged.

As animal Parasites agent for preventing and eliminating, for biological such as the ectoparasitism of the body surface that parasitizes host animal (back of the body, oxter, abdomen, hip inboard etc.) or parasitize in the body of host animal the preventing and kill off effectively of endophyte biology of (stomach, intestinal tube, lung, heart, liver, blood vessel, subcutaneous, Lymphoid tissue etc.), wherein, preventing and kill off effectively outside Parasites.

Biological as ectoparasitism, can list mite such as the animal parastic, flea etc.Such kind is very many, is difficult to all list, and lifts an example wherein.

As animal parasitics mite, can list for example boophilus microplus (Boophilus microplus), brown dog tick (Rhipicephalus sanguineus), haemaphysalis longicornis (Haemaphysalislongicornis), haemaphysalis flava (Haemaphysalis flava), haemaphysalis campanulata (Haemaphysaliscampanulata), haemaphysalis conicinna (Haemaphysalis concinna), Haemaphysalis japonica (Haemaphysalis japonica), Haemaphysalis kitaokai, Haemaphysalis ias, ixodes ovatus (Ixodes ovatus), Ixodes japonensis (Ixodes nipponensis), ixodes persulcatus (Ixodes persulcatus), tortoise shape flower tick (Amblyomma testudinarium), Haemaphysalis megaspinosa, dermacentor reticulatus (Dermacentor reticulatus), the hard tick class that Dermacentor taiwanesis is such; Dermanyssus gallinae (Dermanyssus gallinae), northern fowl mite (Ornithonyssus sylviarum), the such northern fowl mite class of capsule fowl thorn mite (Ornithonyssus bursa), Eutrombicula wichmanni, leptotrombidium akamushi (Leptotrombidium akamushi), leptotrombidium pallidium (Leptotrombidiumpallidum), Fuji trombiculid (Leptotrombidium fuji), Leptotrombidium tosa, Neotrombicula autumnalis, Eutrombicula alfreddugesi, the trombiculid class that Heleniculamiyagawai is such; Rabbit hair worm (Cheyletiella yasguri), cheyletiella parasitovorax (Cheyletiella parasitivorax), the such cheyletid mite class of Cheyletiella blakei; Rabbit ear tsutsugamushi mite (Psoroptes cuniculi), ox foot mite (Chorioptes bovis), dog notoedres cati (Otodectescynotis), itch mite (Sarcoptes scabiei), the such itch mite class of cat back of the body anus mite (Notoedres cati); The demodicid mite class that demodicidosis (Demodex canis) is such etc.Wherein, it is effective especially for preventing and kill off hard tick class etc. to contain the animal Parasites agent for preventing and eliminating of the compounds of this invention.

As flea, can list the aptery insect of ectoparasitism that for example belongs to Siphonaptera (Siphonaptera), more specifically can list the flea class that belongs to Pulicidae (Pulicidae), european mouse flea section (Ceratephyllus) etc.As the flea class that belongs to Pulicidae, can list such as ctenocephalides canis (Ctenocephalidescanis), ctenocephalides felis (Ctenocephalides felis), Pulex irritans (Pulex irritans), chicken flea (Echidnophaga gallinacea), Xanthopsyllacheopis (Xenopsylla cheopis), leptopsylla musculi (Leptopsylla segnis), ceratophyllus fasciatus (Nosopsyllus fasciatus), ceratophyllus anisus (Monopsyllus anisus) etc.Wherein, the animal Parasites agent for preventing and eliminating that contains the compounds of this invention is effective for preventing and kill off the flea class, particularly ctenocephalides canis, ctenocephalides felis etc. that belong to Pulicidae.

Ectoparasitism as other is biological, can list for example blind lice of ox, horse sucking louse, sheep lice, proboscis ox louse, the such lice class of head louse; Dog nibble mao lice such sting lice; Sucking blood property Diptera pest that horsefly, grasshopper, buffalo gnat are such etc.In addition, biological as endophyte, can list for example lung worm, whipworm, the strong nematode of tubercle, stomach entozoa, roundworm, the such threadworms of filaria class; Bothriocephalus linguloides, a wide strobilization tapeworm, multiple hole tapeworm, multiceps, the living tapeworm of bag, wrap the such tapeworms of tapeworm more; Schistosoma japonicum, the such trematodes of sheet fluke; The protozoon that sarcocystis in the coccidia, plasmodium, intestines, toxoplasma gondii, Cryptosporidium are such etc.

As host animal, can list various pets, domestic animal, poultry etc., more particularly, can list dog, cat, mouse, rat, hamster, cavy, squirrel, rabbit, ferret, bird (such as dove, parrot, nine official birds, mannikin, parrot, lonchura striata, canary bird etc.) ox, horse, pig, sheep, duck, chicken etc.Wherein, contain the animal Parasites agent for preventing and eliminating of the compounds of this invention, for preventing and kill off harmful organism, particularly the ectoparasitism biologically effective that parasitizes pet or domestic animal.Effective especially for dog, cat, ox or horse in pet or domestic animal.

When the compounds of this invention uses as animal Parasites agent for preventing and eliminating, can directly use, or be that the various forms of pulvis, granule, tablet, powder, capsule, liquor, emulsion, aqueous suspension agent, oiliness suspension agent etc. are used with suitable auxiliary preparation.And, beyond the above-mentioned dosage form, as long as be fit to purpose of the present invention, also can be all dosage forms that in common this field, use.As the auxiliary that in preparation, uses, can list as the preparation tensio-active agent of auxiliary illustrative anionic species or the tensio-active agent of nonionic class of above-mentioned agriculture and garden with noxious organism control agent; The tensio-active agent of the cationic that cetyl trimethylammonium bromide is such; Water, acetone, acetonitrile, monomethyl ethanamide, N,N-DIMETHYLACETAMIDE, dimethyl formamide, 2-Pyrrolidone, METHYLPYRROLIDONE, kerosene, tri acetylacetonate, methyl alcohol, ethanol, Virahol, benzylalcohol, ethylene glycol, propylene glycol, polyoxyethylene glycol, liquid polyoxyethylene glycol, butyldiglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, glycol ether n-butyl ether, dipropylene glycol monomethyl ether, the such solvent of dipropylene glycol n-butyl ether; Butyl hydroxyanisole, butylhydroxy toluene, xitix, pyrosulphite hydrogen sodium, propyl gallate salt, the such antioxidant of Sulfothiorine; The such tunicle of the multipolymer of polyvinylpyrrolidone, polyvinyl alcohol, vinyl-acetic ester and vinyl pyrrolidone forms agent; As preparation auxiliary illustrative vegetables oil or the mineral oil of above-mentioned agriculture and garden with noxious organism control agent; Carrier that lactose, sucrose, glucose, starch, flour, Semen Maydis powder, soybean oil meal, defatted rice bran, calcium carbonate, other commercially available feedstuff raw material are such etc.The various compositions of these auxiliarys only otherwise break away from purpose of the present invention, can suitably be selected one kind or two or more use.In addition, also can be from this field known substance beyond the above-mentioned auxiliary suitable choice for use, and then, suitable choice for use in the various auxiliarys that can from above-mentioned agriculture and garden field, use etc.

The mixing ratio of the compounds of this invention and various auxiliarys, be generally 0.1: 99.9～about 90: 10.When reality is used these preparations, can directly use, or after the thinner of water etc. is diluted to normality, adds as required various developping agents (tensio-active agent, vegetables oil, mineral wet goods) and use.

Can orally give host animal with the compounds of this invention by oral or non-.As mouth medication, can list such as the tablet that contains the compounds of this invention, liquor, capsule, pancake, biscuit, meat foam, other the method for feed etc.As non-mouth medication, for example can list, the compounds of this invention is made suitable preparation after, the method that is injected in vivo by intravenous administration, intramuscular administration, intradermal administration, subcutaneous administration etc.; Process (spot-on), water and drench the method that (pour-on), spraying processing etc. are administered to body surface of processing by drop; Resin sheet that will contain the compounds of this invention etc. is imbedded subcutaneous method of host animal etc.

The compounds of this invention is for the dosage of host animal, according to medication, administration purpose, disease symptoms etc. and different, but usually take with respect to the 1Kg body weight of host animal as the ratio administration of 0.01mg～100g, preferred 0.1mg～10g be suitable.

The present invention also comprises the method for control based on the harmful organism of medication as described above or dosage, particularly the method for control of ectoparasitism biology or endophyte biology.

In addition, in the present invention, sometimes by above-mentioned harmful organism of preventing and kill off like that the animal parasitics, the various diseases of the host animal that can prevent or treat so cause.The present invention also comprises the method for the Animal diseases that the prevention that contains the Animal diseases that the compounds of this invention causes as the zooparasite of effective constituent or therapeutical agent and prevention or treatment zooparasite cause like this.

When the compounds of this invention is used as animal Parasites agent for preventing and eliminating, can use with simultaneously or and with various vitaminss, mineral substance class, amino acids, nutrition agent, zymin, antipyretic, tranquilizer, antiphlogistic, sterilant, tinting material, perfume compound, sanitas etc. with auxiliary.In addition, can use with as required or and with other various animal drugs or agricultural chemicals, such as wormer, anticoccidiosis medicine, sterilant, miticide, flea killing agent, nematocides, sterilant, antiseptic-germicide etc., such occasion shows more excellent effect sometimes.The present invention comprise use with or and used the mixing Pesticidal composition of various compositions as described above, also comprise in addition the method for control, particularly ectoparasitism biology of the harmful organism of using said composition or the method for control of endophyte biology.

The preferred configuration of the several the compounds of this invention of following illustration.In the illustrative form, for following (1)～(8) but appropriate combination arbitrarily more than 2 and also is the preferred configuration of the compounds of this invention based on the compound of this combination.In addition, contain following compound as the noxious organism control agent of effective constituent, agriculture and garden with noxious organism control agent, desinsection, kill the agent for preventing and eliminating of mite or nematocides, animal Parasites agent for preventing and eliminating, animal ectoparasitism biology, prevention or the therapeutical agent of Animal diseases that Parasites causes, also be preferred configuration of the present invention.In addition, the method that the significant quantity of using following compound is prevented and kill off harmful organism also is preferred configuration of the present invention.But the present invention is not limited thereto.

(1) R ¹At least 1 replace and this R at 4 ¹Compound for the above-mentioned formula (I) of fluorine atom or chlorine atom.

(2) R ¹At least 1 replace and this R at 4 ¹Compound for the above-mentioned formula (I) of chlorine atom.

(3) R ¹At least 1 replace and this R at 4 ¹For alkyl, haloalkyl, alkenyl, halogenated alkenyl, alkynyl, halo alkynyl, alkoxyl group, halogenated alkoxy, alkyl-carbonyl, halogenated alkyl carbonyl, alkoxy carbonyl, halo alkoxy carbonyl, can substituted phenyloxycarbonyl, the compound of the above-mentioned formula (I) of nitro or formyl radical.

(4) R ²Compound for the above-mentioned formula (I) of halogen, haloalkyl, halogenated alkoxy.

(5) R ³Compound for the above-mentioned formula (I) of halogen.

(6) R ³Be halogen, and the compound of 3-or the single replacement of 5-or the disubstituted above-mentioned formula of 3,5-(I).

(7) Y is the compound of the above-mentioned formula (I) of cyclopropyl.

(8) Y is cyclopropyl, and this cyclopropyl is selected from the compound of the above-mentioned formula (I) that 1～5 substituting group in the group that halogen, alkyl and haloalkyl form replaces.

(9) R ¹Be halogen, alkyl, haloalkyl, alkyl-carbonyl or formyl radical; R ²Be halogen, haloalkyl or halogenated alkoxy; R ³Be halogen or haloalkyl; The alkyl of A for being replaced by Y; The cyclopropyl that Y replaces for 1 substituting group in the group that can be selected from halogen and alkyl composition at least; M is 1 or 2; N is 0; Q is the compound of 1 above-mentioned formula (I).

(10) R ¹Replace or the two replacements of 2,4-R for 2-is single ¹Compound for 3-mono-substituted above-mentioned (9) record.

(11) R ¹Be halogen, alkyl or haloalkyl, R ²Be halogen, haloalkyl or halogenated alkoxy, R ³Be halogen, the alkyl of A for being replaced by Y; Y is cyclopropyl; M is 2; N is 0; Q is the compound of 1 above-mentioned formula (I).

(12) R ¹Being that 2,4-is two replaces R ³Compound for 3-mono-substituted above-mentioned (11) record.

(13) 4 R ¹Compound for above-mentioned (12) of chlorine atom record.

(14) formula (I) is formula (I-1), and R ^1aBe halogen or alkyl; R ^1bAnd R ^1dBe respectively hydrogen atom; R ^1cFor alkyl, haloalkyl, alkenyl, halogenated alkenyl, alkynyl, halo alkynyl, alkoxyl group, halogenated alkoxy, alkyl-carbonyl, halogenated alkyl carbonyl, alkoxy carbonyl, halo alkoxy carbonyl, can substituted phenyloxycarbonyl, nitro or formyl radical; R ²Be halogen, haloalkyl or halogenated alkoxy; R ^3aBe halogen or haloalkyl; R ^3b, R ^3cAnd R ^3dBe respectively hydrogen atom; The alkyl of A for being replaced by Y; The cyclopropyl that Y replaces for 1～5 substituting group in the group that can be selected from halogen, alkyl and haloalkyl composition; N is 0 compound.

[changing 5]

(15) R ^1cCompound for above-mentioned (14) of haloalkyl, alkyl-carbonyl or formyl radical record.

(16) R ^1cCompound for above-mentioned (14) of haloalkyl record.

(17) Y is the compound of above-mentioned (14) record of cyclopropyl.

(18) formula (I) is formula (Ia), and R ¹Be halogen or alkyl; R ²And R ³Be respectively halogen or-CF ₃The alkyl of A for being replaced by Y; Y is can be by the C3-4 cycloalkyl of halogen or alkyl replacement; M is 1 or 2; N is 0 compound.

[changing 6]

(19) formula (I) is above-mentioned formula (Ia), and R ¹Be halogen or alkyl; R ²And R ³Respectively independent be halogen or-CF ₃A is-X-Y; X is alkylidene group; Y is can be by the C3-4 cycloalkyl of halogen or alkyl replacement; M is 1 or 2; N is 0 or 1 compound.

Embodiment

Following notebook inventive embodiment, but the present invention is not limited to this.At first put down in writing the synthesis example of the compounds of this invention.

Synthesis example 1

N-[6-[[(encircles the third methyl) amino] carbonyl]-the 2-aminomethyl phenyl]-1-(3-chloro-2-pyridyl)-3-(trifluoromethyl)-1H-pyrazoles-5-methane amide (the aftermentioned compound N is o.1) synthetic

Encircle to 0.8g in the mixed solution of the third methylamine hydrochloride and 40ml tetrahydrofuran (THF), ice-cold lower slowly drip the 1.49g triethylamine after, stirred 30 minutes under the room temperature.Then slowly drip the 2-[1-(3-chloro-2-pyridyl) of 1g-3-(trifluoromethyl)-1H-pyrazoles-5-yl]-8-methyl-4H-3, the mixed solution of 1-benzoxazine-4-ketone and 10ml tetrahydrofuran (THF).After dripping termination, under refluxing, make mixing solutions reaction 4 hours.Behind the reaction terminating, heat up in a steamer desolventizing under the decompression, adding ethyl acetate and water extract in residue.Then water and saturated brine washing organic layer add anhydrous magnesium sulfate drying.Under reduced pressure heat up in a steamer desolventizing, with residue with silica gel column chromatography (elutriant: n-hexane/ethyl acetate=1/1) make with extra care, obtain the object of 199.4 ℃ of 0.54g fusing points.

Synthesis example 2

N-[4-chloro-2-methyl-6-[[Alpha-Methyl-(encircling the third methyl) amino] carbonyl]-phenyl]-3-(trifluoromethyl)-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide (the aftermentioned compound N is o.3) synthetic

In the mixed solution of the Alpha-Methyl of 0.82g-ring the third methylamine hydrochloride and 40ml tetrahydrofuran (THF), ice-cold lower slowly drip the 1.37g triethylamine after, stirred 30 minutes under the room temperature.Then slowly drip the 2-[1-(3-chloro-2-pyridyl) of 1g-3-(trifluoromethyl)-1H-pyrazoles-5-yl]-6-chloro-8-methyl-4H-3, the mixed solution of 1-benzoxazine-4-ketone and 10ml tetrahydrofuran (THF).After dripping termination, under refluxing, make mixing solutions reaction 4 hours.Behind the reaction terminating, heat up in a steamer desolventizing under the decompression, adding ethyl acetate and water extract in residue.Then water and saturated brine washing organic layer add anhydrous magnesium sulfate drying.Under reduced pressure heat up in a steamer desolventizing, with residue with silica gel column chromatography (elutriant: n-hexane/ethyl acetate=1/1) make with extra care, obtain the object of 210.0 ℃ of 0.45g fusing points.

Synthesis example 3

N-[4-chloro-2-methyl-6-[[Alpha-Methyl-(encircling the third methyl) amino] carbonyl]-phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide (the aftermentioned compound N is o.9) synthetic

In the mixed solution of the Alpha-Methyl of 0.65g-ring the third methylamine hydrochloride and 40ml tetrahydrofuran (THF), ice-cold lower slowly drip the 1.07g triethylamine after, stirred 30 minutes under the room temperature.Then slowly drip the 2-[3-bromo-1-(3-chloro-2-pyridyl) of 0.8g-1H-pyrazoles-5-yl]-6-chloro-8-methyl-4H-3, the mixed solution of 1-benzoxazine-4-ketone and 10ml tetrahydrofuran (THF).After dripping termination, under refluxing, make mixing solutions reaction 4 hours.Behind the reaction terminating, heat up in a steamer desolventizing under the decompression, adding ethyl acetate and water extract in residue.Then water and saturated brine washing organic layer add anhydrous magnesium sulfate drying.Under reduced pressure heat up in a steamer desolventizing, with residue with silica gel column chromatography (elutriant: n-hexane/ethyl acetate=1/1) make with extra care, obtain the object of 183.6 ℃ of 0.33g fusing points.

Synthesis example 4

N-[2-bromo-4-chloro-6-[[Alpha-Methyl-(encircling the third methyl) amino] carbonyl]-phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide (the aftermentioned compound N is o.15) synthetic

In the mixed solution of the Alpha-Methyl of 0.6g-ring the third methylamine hydrochloride and 40ml tetrahydrofuran (THF), ice-cold lower slowly drip the 1g triethylamine after, stirred 1 hour under the room temperature.Then slowly drip the 2-[3-bromo-1-(3-chloro-2-pyridyl) of 0.85g-1H-pyrazoles-5-yl]-6-chloro-8-bromo-4H-3, the mixed solution of 1-benzoxazine-4-ketone and 10ml tetrahydrofuran (THF).After dripping termination, under refluxing, make mixing solutions reaction 4 hours.Behind the reaction terminating, heat up in a steamer desolventizing under the decompression, adding ethyl acetate and water extract in residue.Then water and saturated brine washing organic layer add anhydrous magnesium sulfate drying.Under reduced pressure heat up in a steamer desolventizing, with residue with silica gel column chromatography (elutriant: n-hexane/ethyl acetate=1/2) make with extra care, obtain the object of 260.6 ℃ of 0.7g fusing points.

Below, in table 1, enumerate the typical example of the compounds of this invention of above-mentioned formula (I) expression.These compounds can synthesize according to the various manufacture method of above-mentioned synthesis example or the invention described above compound.

In the table 1, No. represents the compound sequence number.In addition, in the table 1, Me represents that methyl, Et represent that ethyl, iPr represent that sec.-propyl, CPr representative ring propyl group, CBu representative ring butyl, Ph represent phenyl.In addition, in the table 1, A1 represents-CH ₂-[CPr], A2 represent-CH (Me)-[CPr], A3 represent-CH ₂-[2-Me-CPr], A4 represent-CH ₂-[2,2-Cl ₂-1-Me-CPr], A5 represents-CH ₂-[1-Me-CPr], A6 represent-CH (Me)-[CBu].In table 1,2-Me-CPr represents 2 methyl substituted cyclopropyl, CO in addition ₂The phenyloxycarbonyl that 4 chlorine atoms of Ph (4-Cl) expression phenyl replace, other same records are taken this as the standard.

In addition, in table 1, so long as not writing out especially, then n is 0.

Table 1

No.

R 1a

R 1b

R 1c

R 1d

R 2

R 3a

R 3b

R 3c

R 3d

A

Physical property (fusing point ℃)

1

Me

H

H

H

CF 3

Cl

H

H

H

A1

199.4

2

Me

H

Cl

H

CF 3

Cl

H

H

H

A1

216.4

3

Me

H

Cl

H

CF 3

Cl

H

H

H

A2

210.0

4

Me

H

Cl

H

CF 3

Cl

H

H

H

A3

5

Me

H

Cl

H

CF 3

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

CF 3

Cl

H

H

H

A5

161.2

11

Br

H

Cl

H

CF 3

Cl

H

H

H

A2

158.2

12

I

H

Br

H

CF 3

Cl

H

H

H

A2

145.5

13

Me

H

Cl

H

CF 3

Cl

H

H

H

A2

230.9

14

Cl

H

Cl

H

CF 3

Cl

H

H

H

A2

238.8

15

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

CF 3

Cl

H

H

H

A2

220.1

19

I

H

Cl

H

CF 3

Cl

H

H

H

A2

241.0

20

Cl

H

F

H

CF 3

Cl

H

H

H

A2

214.0

21

I

H

I

H

CF 3

Cl

H

H

H

A2

251.9

22

Br

H

F

H

Br

Cl

H

H

H

A2

219.2

23

Me

H

Cl

H

CF 3

Br

H

H

H

A2

162-164

24

Me

H

Cl

H

Cl

CF 3

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

CF 3

Cl

H

H

H

A2

30

I

H

F

H

CF 3

Cl

H

H

H

A2

31

F

H

F

H

CF 3

Cl

H

H

H

A2

32

F

H

F

H

Br

Cl

H

H

H

A2

33

Me

H

F

H

CF 3

Cl

H

H

H

A2

34

Me

H

F

H

Br

Cl

H

H

H

A2

35

Me

H

CO 2Me

H

Br

Cl

H

H

H

A2

36

Me

H

CO 2-iPr

H

Br

Cl

H

H

H

A2

Table 1 (continuing)

No.

R 1a

R 1b

R 1c

R 1d

R 2

R 3a

R 3b

R 3c

R 3d

A

Physical property (fusing point ℃)

37

Me

H

CO 2Ph

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

COCH 3

H

CF 3

Cl

H

H

H

A2

143.4

41

Me

H

CHO

H

CF 3

Cl

H

H

H

A2

152.3

42

Me

H

CHF 2

H

CF 3

Cl

H

H

H

A2

212.9

43

Me

H

CHF 2

H

Br

Cl

H

H

H

A2

44

Me

H

CHF 2

H

Cl

Cl

H

H

H

A2

45

Et

H

Cl

H

CF 3

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

NO 2

H

CF 3

Cl

H

H

H

A2

197.9

49

Me

H

NO 2

H

Br

Cl

H

H

H

A2

50

Me

H

NO 2

H

Cl

Cl

H

H

H

A2

51

Me

H

CF 3

H

Br

Cl

H

H

H

A2

52

Me

H

CF 3

H

Cl

Cl

H

H

H

A2

53

Me

H

CF 3

H

CF 3

Cl

H

H

H

A2

54

CF 3

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

CF 3

Cl

H

H

H

A2

57

Me

H

OMe

H

Cl

Cl

H

H

H

A2

58

OCHF 2

H

Cl

H

Cl

Cl

H

H

H

A2

59

OCHF 2

H

Cl

H

Br

Cl

H

H

H

A2

60

OCHF 2

H

Cl

H

CF 3

Cl

H

H

H

A2

61

CHF 2

H

Cl

H

CF 3

Cl

H

H

H

A2

62

CHF 2

H

Cl

H

Br

Cl

H

H

H

A2

63

CHF 2

H

Cl

H

Cl

Cl

H

H

H

A2

64

Me

H

CH＝CH 2

H

CF 3

Cl

H

H

H

A2

65

Me

H

C≡CH

H

CF 3

Cl

H

H

H

A2

66

Me

H

Cl

H

CF 3

Cl

H

H

H

A6

67

Me

H

COCF 3

H

Br

Cl

H

H

H

A2

68

Me

H

CH＝CCl 2

H

CF 3

Cl

H

H

H

A2

69

Me

H

C≡CI

H

CF 3

Cl

H

H

H

A2

70

Me

H

CO 2Ph(4-Cl)

H

Br

Cl

H

H

H

A2

71

Me

H

CO 2Ph(4-Me)

H

CF 3

Cl

H

H

H

A2

72

Me

H

CO 2Ph(4-NO 2)

H

CF 3

Cl

H

H

H

A2

73

Me

H

CO 2Ph(4-CN)

H

CF 3

Cl

H

H

H

A2

74

Me

H

CO 2Ph(4-SMe)

H

CF 3

Cl

H

H

H

A2

75

Et

H

Cl

H

OCH 2CF 3

Cl

H

H

H

A2

76

Me

H

NO 2

H

OCH 2CF 3

Cl

H

H

H

A2

77

Me

H

CHF 2

H

CF 3

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

Table 1 (continuing)

Below put down in writing test example

Test example 1 for prodenia litura ( Spodoptera Litura) effect test

Be formulated as in the liquid of 50ppm or 3.1ppm in the concentration with the compounds of this invention, with 10 seconds of blade dip treating of wild cabbage, then air-dry.Wet filter paper is layered in the Petri dish of diameter 9cm, air-dry blade is placed thereon.The Spodoptera litura larvae in 10 2～3 ages is put thereon, and closing the lid is positioned in the band illumination thermostatic chamber.Put behind the worm and to judge life and death on the 5th day, ask mortality ratio according to following calculating formula.Unusual worm is also regarded death as in addition.When asking the mortality ratio of 50ppm for above-claimed cpd No.8,20～22,25,41,91～93 and 96, all compound exhibits the high preventive effect more than 90%, in addition, when asking the mortality ratio of 3.1ppm for above-claimed cpd No.1～3,5,9～19,23,24,38～40,42,80,81 and 90, all compound exhibits the high preventive effect more than 90%.

Mortality ratio (%)=(death toll/put borer population) * 100

Test example 2 for Bemisia argentifolii ( Bemisia Argentifoli) effect test

Excise in the potted plant cucumber of other leaves at residual 1 the 1st leaf, put into the adult of Bemisia argentifolii and make and lay eggs about 8 hours.25 ℃ band illumination thermostatic chamber in place 7～10 day thereafter.Behind the investigation hatching larva number, be formulated as in the liquid of 200ppm or 50ppm parasitic blade dip treating about 10 seconds in the concentration with the compounds of this invention, then air-dry.Place 10～14 days in 25 ℃ band illumination thermostatic chamber after, investigation mature larvae number and pupa number utilize following calculating formula to ask the valency of preventing and kill off.For above-claimed cpd No.11 and 21 ask 200ppm prevent and kill off valency the time, shown the high preventive effect more than 80%, in addition, for above-claimed cpd No.3,9,12,14～20,22,38 and 39 ask 50ppm prevent and kill off valency the time, all compound exhibits the high preventive effect more than 80%.

Prevent and kill off valency (%)=(1-((Ta * Cb)/(Tb * Ca))) * 100

Ta: the mature larvae number after treatment zone is processed+pupa number

Tb: the hatching larva number before treatment zone is processed

Ca: the mature larvae number after the non-processor district processes+pupa number

Cb: the hatching larva number before the non-processor district processes

Test example 3 for black peach aphid ( Myzus Persicae) effect test

After only the petiole of the potted plant eggplant of residual 1 this leaf is coated with adhesive agent, put into the aptery viviparous female adult worm of 2～3 black peach aphids at this this leaf.Put after worm removes adult after 2 days investigation larva number.After being formulated as in the liquid of 800ppm about 10 seconds of eggplant leaf dip treating of this parasitized larvae, being air-dry, the concentration with the compounds of this invention is positioned in 25 ℃ the band illumination thermostatic chamber.Process 5 days " Invest, Then Investigate " existence borer populations, utilize following calculating formula to ask mortality ratio.When asking mortality ratio for above-claimed cpd No.2,9,11,14～18,20,22,23,38,39,42 and 90, all compound exhibits the high preventive effect more than 90%.

Mortality ratio (%)=(1-(existence borer population/processing borer population)) * 100

Test example 4 for cotten aphid ( Aphis Gossypii) effect test

After only the petiole of the potted plant eggplant of residual 1 this leaf is coated with adhesive agent, put into the aptery viviparous female adult worm of 3～4 cotten aphids at this this leaf.Put worm and remove adult after 2 days, investigation larva number.After being formulated as in the liquid of 50ppm about 10 seconds of eggplant leaf dip treating of this parasitized larvae, being air-dry, the concentration with the compounds of this invention is positioned in 25 ℃ the band illumination thermostatic chamber.Process 5 days " Invest, Then Investigate " existence borer populations, ask equally mortality ratio with above-mentioned test example 3.When asking mortality ratio for above-claimed cpd No.16,18 and 22, all compound exhibits the high preventive effect more than 90%.

Test example 5 for Liriomyza trifolii ( Liriomyza Trifolii) effect test

Be formulated as in the liquid of 25ppm or 12.5ppm in the concentration with the compounds of this invention, with producing equably about 10 seconds of blade dip treating of Kidney bean of the ovum of Liriomyza trifolii, then air-dry.Wet filter paper is layered in the plastic cup of diameter 9cm, high 4cm, the blade of air-dry Kidney bean is placed thereon.Close the lid the band illumination thermostatic chamber that be positioned over 25 ℃ in thereafter.Process 6～8 days " Invest, Then Investigate "s existence mature larvae number and pupa number, utilize following calculating formula to ask the valency of preventing and kill off.For above-claimed cpd No.9,14 and 23 ask 25ppm prevent and kill off valency the time, all compound exhibits the high preventive effect more than 90%, in addition, for above-claimed cpd No2,3,11,12,15～18,20 and 22 ask 12.5ppm prevent and kill off valency the time, all compound exhibits the high preventive effect more than 90%.

Prevent and kill off valency (%)=(1-((the mature larvae number for the treatment of zone+pupa number)/(the mature larvae number in non-processor district+pupa number))) * 100

Test example 6 for palm thrips ( Thrips Palmi) effect test

Residual 1 the 1st leaf and excise other leaf only on potted plant cucumber.Be formulated as in the liquid of 50ppm residual about 10 seconds of leaf section dip treating in the concentration with the compounds of this invention, then air-dry.Thereafter, the blade of the cucumber of 1 instar larvae parasitism is placed on above-mentioned processing leaf above.Second day, the blade of excision cucumber, and the larva number of processing on the leaf is transferred in investigation.Wet filter paper is layered in the plastic cup of diameter 9cm, high 4cm, the processing leaf that has cut is placed thereon.Close the lid the band illumination thermostatic chamber that be positioned over 25 ℃ in thereafter.Process 12～15 days " Invest, Then Investigate " existence borer populations, similarly ask the valency of preventing and kill off with above-mentioned test example 2.Ask when preventing and kill off valency for above-claimed cpd No.11,12,16,22,38 and 39, all compound exhibits the high preventive effect more than 90%.

Test example 7 for ladybug of eggplant 28 stars ( Epilachna Vigintioctopunctata) effect test

Be formulated as in the liquid of 25ppm or 12.5ppm the blade dip treating of eggplant about 10 seconds in the concentration of the compounds of this invention, then air-dry.Wet filter paper is layered in the plastic cup of diameter 9cm, high 4cm, the blade of air-dry eggplant is placed thereon.The ladybug of eggplant 28 stars larva in 5 1～2 ages is put thereon, in the band illumination thermostatic chamber that is positioned over 25 ℃ that closes the lid.Put behind the worm and to judge life and death on 4th～6, similarly ask mortality ratio with above-mentioned test example 1.Unusual worm is also regarded death as in addition.When asking the mortality ratio of 25ppm for above-claimed cpd No.9 and 11, all compound exhibits the high preventive effect more than 90%, in addition, when asking the mortality ratio of 12.5ppm for above-claimed cpd No.3,16,22,38 and 39, all compound exhibits the high preventive effect more than 90%.

Test example 8 for housefly ( Musca Domestica) effect test

10g bait substratum is packed into behind the plastic cup of diameter 6cm, high 3cm, add 10ml the concentration of the compounds of this invention is formulated as the liquid of 200ppm, mix.Put into 20 or 30 hatching 4 day old larva, close the lid and in 25 ℃ band illumination thermostatic chamber, placed 15～16 days.Its " Invest, Then Investigate " adult number utilizes following calculating formula to ask the emergence inhibiting rate.When asking the emergence inhibiting rate for above-claimed cpd No.3,9,11,12 and 14～20, all compound exhibits the high preventive effect more than 90%.

Emergence inhibiting rate (%)=(1-(become borer population/put borer population)) * 100

Test example 9 for Coptotermes formosanus Shtrari． ( Coptotermes Formosanus) effect test

Filter paper is layered in the glass culture dish of diameter 9cm, and with 1ml the liquid that the concentration of the compounds of this invention is formulated as 50ppm is processed., put into worker ant and 1 soldier ant of 10 boss termites, close the lid and in 25 ℃ band illumination thermostatic chamber, place thereafter.Process the death toll of 6 days " Invest, Then Investigate " worker ants, and utilize following calculating formula to ask mortality ratio.For above-claimed cpd No.3,9,11,12,14～16, and 22 when asking mortality ratio, all compound exhibits the high preventive effect more than 90%.

Mortality ratio (%)=(the dead borer population of worker ant/10) * 100

Test example 10 prodenia lituras ( Spodoptera Litura) test of infiltration transitivity

The liquid that the concentration of the compounds of this invention is formulated as 80ppm or 200ppm with 10ml is processed the root of the potted plant wild cabbage of 5～6 leaf phases.Filter paper is layered in the Petri dish of diameter 9cm, places and process the cabbage leaves that cuts after 10 days.The Spodoptera litura larvae in 10 2～3 ages is put into wherein, in the band illumination thermostatic chamber that is positioned over 25 ℃ that closes the lid.Put behind the worm and to judge life and death on the 4th～5 day, similarly ask mortality ratio with above-mentioned test example 1.In addition, unusual worm is also regarded death as.When asking the mortality ratio of 800ppm for above-claimed cpd No.8, all compound exhibits the high preventive effect more than 90%, in addition, when asking the mortality ratio of 200ppm for above-claimed cpd No.3,9,11,16,18 and 22, all compound exhibits the high preventive effect more than 90%.

Test example 11 for haemaphysalis longicornis ( Haemaphysalis Longicornis) the test of pesticide effectiveness

With micropipet with the acetone soln of 1ml test compound (concentration: 10 μ g/ml) drip and process 9cm diameter culture dish.On the other hand, district in contrast is equally with the processing of dripping of 1ml acetone.After the culture dish inner face drying, put into about 100 young tick, cover and seal with elastic ribbon with polyethylene sheets.During thereafter except observation, culture dish is left standstill under 25 ℃ of constant temperature, relative humidity 100%, permanent dark condition.Begin whenever to observe the roll tick number behind the record contact medicament through (after 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 45 minutes, 1 hour, 2 hours, 4 hours, 6 hours and 24 hours) behind the certain hour from young tick being put into culture dish.Above operation is carried out 2 times repeatedly.

Utilize following A bbott updating formula to proofread and correct roll rate when respectively observing, then draw a probit-time straight line, then ask the half roll time (KT50 value).The KT50 value of each test compound, above-claimed cpd No.3 is that 9 minutes and 8 minutes, above-claimed cpd No.9 are 7.5 minutes and 6 minutes, and following comparative compound A is 80 minutes and 40 minutes, following compd B is 120 minutes and 80 minutes.

Proofread and correct roll rate (%)=[the non-roll rate of (the non-roll rate of the non-roll rate-treatment zone of check plot)/check plot] * 100

Comparative compound A is as the compound 484 among the WO03/24222, the Compound 497 among the WO03/15518, the following compound of compound 2 among the WO03/15519.

[changing 7]

Comparative compound A

Comparative compound B is as the compound 509 among the WO03/24222, the compound 530 among the WO03/15518, the following compound of compound 27 among the WO03/15519.

[changing 8]

Comparative compound B

Test example 12 for cat flea ( Ctenocephalides Felis) the test of pesticide effectiveness

Be formulated as acetone soln Glass tubing (internal diameter 2.6cm, the floorage 5.3cm level and smooth to the bottom surface of the compounds of this invention of 5.3ppm with 0.5ml ³, high 12cm) processing of dripping.Acetone is evapotranspired, form the dry film that the compounds of this invention is contained in the bottom surface.The adult (sprouting wings rear 5 days with the interior adult of not sucking blood) of 10 cat fleas (Ctenocephalides felis) is put into wherein.And compound of the present invention is exposed.Test repeats with three times.

Expose the life and death of judging flea after 48 hours, similarly ask mortality ratio with above-mentioned test example 1.When asking mortality ratio for above-claimed cpd No.16, shown the high preventive effect more than 90%.

Below put down in writing formulation example.

Formulation example 1

(1) the compounds of this invention 20 weight parts

(2) clay 72 weight parts

(3) sodium lignosulfonate 8 weight parts

Evenly mix above composition and make wettable powder.

Formulation example 2

(1) the compounds of this invention 5 weight parts

(2) talcum 95 weight parts

Evenly mix above composition and make pulvis.

Formulation example 3

(1) the compounds of this invention 20 weight parts

(2) N, N '-N,N-DIMETHYLACETAMIDE 20 weight parts

(3) polyoxyethylene alkyl phenyl ether 10 weight parts

(4) dimethylbenzene 50 weight parts

Evenly mix, dissolve above composition and make emulsion.

Formulation example 4

(1) clay 68 weight parts

(2) sodium lignosulfonate 2 weight parts

(3) polyxyethylated aromatic yl acid ester 5 weight parts

(4) fine particle silica 25 weight parts

To make wettable powder behind above each composition of part by weight mixing of 4: 1 and the compounds of this invention.

Formulation example 5

(1) the compounds of this invention 50 weight parts

(2) oxidation polyoxyethylene alkylphenyl base phosphoric acid ester-trolamine 2 weight parts

(3) polysiloxane 0.2 weight part

(4) water 47.8 weight parts

In the stoste of evenly mixing, pulverize above composition, further add

(5) poly carboxylic acid sodium 5 weight parts

(6) anhydrous sodium sulphate 42.8 weight parts

And evenly mix, granulation, dry after the granulation wettable powder.

Formulation example 6

(1) the compounds of this invention 5 weight parts

(2) polyoxyethylene octyl phenyl ether 1 weight part

(3) polyoxyethylated phosphoesterase 30 .1 weight part

(4) granular calcium carbonate 93.9 weight parts

Evenly mix in advance (1)～(3), after an amount of acetone diluted, be sprayed on (4), remove the agent of acetone granulation.

Formulation example 7

(1) the compounds of this invention 2.5 weight parts

(2) METHYLPYRROLIDONE 2.5 weight parts

(3) soybean oil 95.0 weight parts

Evenly mix, dissolve above composition and make micro-spraying agent (ultra low volumeformulation).

Formulation example 8

(1) the compounds of this invention 40 weight parts

(2) oxidation polyoxyethylene alkylphenyl base phosphoric acid ester-trolamine 2 weight parts

(3) polysiloxane 0.2 weight part

(4) Zanthan gum 0.1 weight part

(5) ethylene glycol 5 weight parts

(6) water 52.7 weight parts

Make the aqueous suspension agent behind evenly mixing, the above composition of pulverizing.

Formulation example 9

(1) the compounds of this invention 10 weight parts

(2) diethylene glycol monoethyl ether 90 weight parts

Make solution after evenly mixing above composition.

In addition, as the disclosed content of specification sheets of the present invention, be incorporated herein as the application and advocated Japanese patent application 2004-041295 number (on February 18th, 2004 is to the Japan Office application), Japanese patent application 2004-133722 number (on April 28th, 2004 is to the Japan Office application), the Japanese patent application 2004-261507 number (on September 8th, 2004 is to the Japan Office application) of basis for priority and the specification sheets full content of Japanese patent application 2004-295778 number (on October 8th, 2004 is to the Japan Office application).

Claims (12)

1. anthranilamides or its salt of a formula (I) expression,

In the formula, R ¹Be halogen, C1～6 alkyl, C1～6 haloalkyls, C1～6 alkyl-carbonyls, nitro or formyl radical; R ²And R ³Independent respectively is halogen, C1～6 haloalkyls or C1～6 halogenated alkoxies; A is the C1 that replaced by Y～6 alkyl; The C3 cycloalkyl that Y replaces for 1 substituting group in the group that can be selected from halogen and C1～6 alkyl composition at least; M is 0～4; N is 0; Q is 0～4, and condition is (1) R ¹Fluorine atom, chlorine atom, bromine atoms or methyl and other R for 2 replacements of phenyl ring ¹During for the halogen of 4 replacements of phenyl ring, this halogen of 4 is fluorine atom or chlorine atom, (2) N-[2-bromo-4-chloro-6-[[Alpha-Methyl-(encircling the third methyl) amino] carbonyl]-phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide except.

2.N-[6-[[(encircle the third methyl) amino] carbonyl]-the 2-aminomethyl phenyl]-1-(3-chloro-2-pyridyl)-3-(trifluoromethyl)-1H-pyrazoles-5-methane amide.

3.N-[4-chloro-2-methyl-6-[[Alpha-Methyl-(encircling the third methyl) amino] carbonyl]-phenyl]-3-(trifluoromethyl)-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide.

4.N-[4-chloro-2-methyl-6-[[Alpha-Methyl-(encircling the third methyl) amino] carbonyl]-phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide.

5. the anthranilamides of a formula (I) expression or the manufacture method of its salt is characterized in that, make the compound of formula (IV) expression and the compound reaction of formula (V) expression,

In the formula, R ¹Be halogen, C1～6 alkyl, C1～6 haloalkyls, C1～6 alkyl-carbonyls, nitro or formyl radical; R ²And R ³Independent respectively is halogen, C1～6 haloalkyls or C1～6 halogenated alkoxies; A is the C1 that replaced by Y～6 alkyl; The C3 cycloalkyl that Y replaces for 1 substituting group in the group that can be selected from halogen and C1～6 alkyl composition at least; M is 0～4; N is 0; Q is 0～4, and condition is (1) R ¹Fluorine atom, chlorine atom, bromine atoms or methyl and other R for 2 replacements of phenyl ring ¹During for the halogen of 4 replacements of phenyl ring, this halogen of 4 is fluorine atom or chlorine atom, (2) N-[2-bromo-4-chloro-6-[[Alpha-Methyl-(encircling the third methyl) amino] carbonyl]-phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide except

In the formula, R ¹, R ², R ³, m, n and q as previously mentioned;

Formula (V): A-NH ₂, in the formula, A as previously mentioned.

6. agriculture and garden noxious organism control agent, it contains anthranilamides claimed in claim 1 or its salt as effective constituent.

A desinsection, kill mite or nematocides, it contains anthranilamides claimed in claim 1 or its salt as effective constituent.

8. animal Parasites agent for preventing and eliminating, it contains anthranilamides claimed in claim 1 or its salt as effective constituent.

9. the agent for preventing and eliminating of an animal ectoparasitism biology, it contains anthranilamides claimed in claim 1 or its salt as effective constituent.

10. prevention or the therapeutical agent of the Animal diseases that cause of a zooparasite, it contains anthranilamides claimed in claim 1 or its salt as effective constituent.

11. an agriculture and garden is used anthranilamides claimed in claim 1 or its salt of significant quantity and is prevented and kill off harmful organism with the method for preventing and kill off harmful organism.

12. the method for preventing and kill off animal body ectoparasitism biology of non-therapeutic purpose is used anthranilamides claimed in claim 1 or its salt of significant quantity and is prevented and kill off.