JP3071962B2 - Pest control composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pesticidally useful agricultural and horticultural composition comprising a combination of a hydrazone compound represented by the general formula (I) or a salt thereof and a known insecticide or fungicide. .

[0002]

2. Description of the Related Art Conventionally, organophosphorus compounds, carbamate compounds and pyrethroid compounds have been used as active ingredients of insecticides. As a result, recently, some pests have resistance to these insecticides. Reached. Therefore, there is a need for insecticides that are effective against resistant pests. The hydrazone compound represented by the general formula (I) or a salt thereof is a novel compound useful as an insecticide,
It has been filed by the present applicant as Japanese Patent Application No. 4-79402.

[0003]

Conventional pest control agents have characteristics in terms of spectrum and effect, however, on the other hand, on the other hand, the effect is not sufficient for specific pests or the residual effect is short and constant. The effect of the period cannot be expected, and depending on the application scene, a practically sufficient control effect may not be exhibited. Further, even if they have excellent control effects, improvements are required from the viewpoint of safety for fish, crustaceans and livestock, and high control effects are required with a small amount of treatment.

[0004]

Means for Solving the Problems As a result of repeated studies to solve these problems, the present inventors have found that a hydrazone compound represented by the general formula (I) or a salt thereof and a known pesticide are used. By combining these, it is possible to control pests that occurred in a certain scene at once, or to reduce the amount of drug used compared to the case where each active ingredient compound is used alone, which is more than expected effect. Were obtained, and the present invention was completed. That is, the present invention provides a compound represented by the general formula (I):

[0005]

Embedded image (Wherein X is a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom or an alkoxy group optionally substituted with a halogen atom, and Y is a halogen atom, R ¹ is a hydrogen atom or an alkyl group, R ² is an alkylcarbonyl group or an alkoxycarbonyl group, and R ¹ and R ² are ^May form a ＣＲCR ³ NR ⁴ R ⁵ group, wherein R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group) or a salt thereof. And an organic phosphorus compound, a carbamate compound, a pyrethroid compound,
Nitro compounds, benzoyl urea compounds, nereistoxin derivatives, hydrazine compounds, heterocyclic compounds, phenyl compounds, silane compounds, juvenile hormone compounds, organochlorine compounds, organometallic compounds, anilide compounds And a pest control composition containing as an active ingredient at least one compound selected from the group consisting of antibiotics.

In the definition of the hydrazone compound represented by the general formula (I), the halogen atom includes a fluorine atom,
A chlorine atom, a bromine atom, an iodine atom, and the alkyl group and the alkyl moiety constituting each radical include those having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, benzyl, hexyl, and the like; They include linear or branched ones. As the salt of the hydrazone compound represented by the general formula (I),
Salts with acidic substances or basic substances are mentioned. Salts with acidic substances include inorganic acid salts such as hydrochloride and sulfate,
Salts with basic substances include salts with inorganic or organic bases such as sodium, potassium, calcium, ammonium and dimethylamine salts. The hydrazone-based compound represented by the general formula (I) has an E-isomer and a Z-isomer due to a hydrazone double bond. Table 1 shows typical examples of the hydrazone-based compound represented by the general formula (I).

[0007]

[Table 1]

In the present invention, examples of pest control agents (hereinafter abbreviated as other active ingredients) combined with the hydrazone compound represented by the above general formula (I) or a salt thereof include the following.

(A) Organic phosphorus compound (A-1) O-4-bromo-2-chlorophenyl O-
Ethyl S-propyl phosphorothioate (generic name: propenophos) (A-2) 2,2-dichlorovinyldimethyl phosphate (generic name: dichlorvos) (A-3) Ethyl 4-methylthio-m-tolyl isopropyl phosphoramidate (generic name) : Phenamiphos) (A-4) O, O-dimethyl O- (4-nitro-m-
(Tolyl) phosphorothioate (generic name: fenitrothion) (A-5) O-ethyl O- (4-nitrophenyl) phenylphosphonothioate (generic name: EPN) (A-6) O, O-diethyl O-2-isopropyl −
6-Methylpyrimidin-4-yl phosphorothioate (generic name: diazinon) (A-7) O, O-dimethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate (generic name: chlorpyrifosmethyl) (A-8 ) O, S-dimethylacetyl phosphoramidothioate (generic name: acephate) (A-9) O-2,4-dichlorophenyl O-ethyl S-propyl phosphorodithioate (generic name: prothiophos) (A-10) ) (RS) -S-sec-butyl O-ethyl 2-oxo-1,3-thiazolidin-3-ylphosphonothioate (generic name: phosthiazate) (A-11) O, O-diethyl O- (5- Phenyl-
3-isoxazolyl) phosphorothioate (generic name: isoxathione) (A-12) O-ethyl O-2-isopropoxycarbonylphenylisopropyl phosphoramidothioate (generic name: isofenphos) (A-13) O, O, O ' , O'-tetraethyl S,
S-methylene di (phosphorodithioate) (generic name: ethion) (A-14) O, O-diethyl S-2-ethylthioethyl phosphorothioate (generic name: disulfoton) (A-15) O-6-ethoxy- 2-ethylpyrimidin-4-yl O, O-dimethyl phosphorothioate (generic name: etrimphos) (A-16) O, O-diethyl O-quinoxaline-2
-Yl phosphorothioate (generic name: quinalphos) (A-17) O, O-Getyl O-3,5,6-trichloro-2-pyridyl phosphorothioate (generic name: chlorpyrifos) (A-18) 2-chloro-1- ( 2,4-dichlorophenyl) vinyl dimethyl phosphate (generic name: dimethylvinphos) (A-19) O, O-dimethyl S-methylcarbamoylmethyl phosphorodithioate (generic name: dimethoate) (A-20) O-ethyl O-4-methylthiophenyl S-propyl phosphorodithioate (generic name: sulfophos) (A-21) S-2-ethylthioethyl O, O-dimethylphosphorodithioate (generic name: thiomethone) (A-22 ) O, O-Dimethyl S-2- (1-methylcarbamoylethylthio) ethyl phosphorothio (Generic name: pamidione) (A-23) (RS)-[O-1- (4-chlorophenyl) pyrazol-4-yl O-ethyl S-propyl phosphorothioate] (generic name: pyraclophos) (A-24) ) A, O-Diethyl-O- (3-oxo-2)
-Phenyl-2H-pyridazin-6-yl) phosphorothioate (generic name: pyridafenthion) (A-25) O-2-Diethylamino-6-methylpyrimidin-4-yl O, O-dimethylphosphorothioate (generic name: pyrimiphosmethyl) ( A-26) 4- (methylthio) phenyldipropyl phosphate (generic name: propaphos) (A-27) S-6-chloro-2,3-dihydro-2-
Oxobenzoxazol-3-ylmethyl O, O-
Diethylphosphorodithioate (generic name: hosalon) (A-28) S- (N-formyl-N-methylcarbamoylmethyl) O, O-dimethylphosphorodithioate (generic name: formothione) (A-29) diethyl ( Dimethoxythiophosphorylthio) succinate (generic name: malathion) (A-30) (Z) -2-chloro-1- (2,4,5-
(A-31) 2-chloro-1- (2,4-dichlorophenyl) vinyldiethyl phosphate (generic name: chlorphenbisphos) (A-32) O-4-cyanophenyl O, O-dimethyl phosphorothioate (generic name: cyanophos) (A-33) dimethyl 2,2,2-trichloro-1-
Hydroxyethylphosphonate (generic name: trichlorfon) (A-34) S-2,3-dihydro-5-methoxy-2
-Oxo 1,3,4-thiadiazol-3-ylmethyl O, O-dimethylphosphorodithioate (generic name:
(A-35) Ethyl-2-dimethoxythiophosphorylthio-2-phenylacetate (generic name: phentoate) (A-36) S-benzyl O, O-diisopropyl phosphorothioate (generic name: iprovenphos) (A-37) ) O-Ethyl SS-diphenyl phosphorodithioate (generic name: edifenphos)

(B) Carbamate compound (B-1) 1-naphthylmethyl carbamate (general name:
Carbaryl) (B-2) 2-Isopropoxyphenylmethyl carbamate (generic name: propoxur) (B-3) 2-Methyl-2- (methylthio) propionaldehyde O-methylcarbamoyl oxime (generic name: aldicarb) (B- 4) 2,3-dihydro-2,2-dimethylbenzofuran-7-ylmethylcarbamate (generic name: carbofuran) (B-5) dimethyl N, N '-[thiobis [(methylimino) carbonyloxy]] bis [ethane (Imidothioate) (generic name: thiodicarb) (B-6) S-methyl N- (methylcarbamoyloxy) thioacetimidate (generic name: mesomil) (B-7) Methyl N, N'-dimethyl-N- (Methylcarbamoyloxy) -1-thio-oxamimidate (generic name: oxamyl) (B- 8) 2-Ethylthiomethylphenylmethylcarbamate (generic name: ethiophencarb) (B-9) 2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate (generic name: pyrimicarb) (B-10) 2 -Sec-butylphenylmethylcarbamate (generic name: fenobcarb) (B-11) 2,2-dimethyl-1,3-benzodioxol-4-yl methylcarbamate (generic name: bendiocarb) (B-12) ethyl N -[2,3-dihydro-2,2
-Dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-β-alaninate (generic name: benfracarb) (B-13) 2,3-dihydro-2,2-dimethyl-7
-Benzofuran-7-yl (dibutylaminothio) methyl carbamate (generic name: carbosulfan) (B-14) butyl 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N, N'-dimethyl- N,
N'-thiodicarbamate (generic name: furatiocarb) (B-15) o-cumenylmethyl carbamate (generic name: isoprocarb) (B-16) m-tolylmethyl carbamate (generic name:
(Metrecarb) (B-17) 3,4-xylylmethylcarbamate (generic name: crisilylcarb) (B-18) 3,5-xylylmethylcarbamate (generic name: XMC)

(C) Pyrethroid compound (C-1) (RS) -α-cyano-3-phenoxybenzyl (RS) -2- (4-chlorophenyl) -3-methylbutyrate (generic name: fenvalerate) (C-2) 3-phenoxybenzyl (1RS, 3RS)
-(1RS, 3SR) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (generic name: permethrin) (C-3) (RS) -α-cyano-3-phenoxybenzyl (1RS, 3RS)-(1RS, 3SR) -3-
(2,2-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (generic name: cypermethrin) (C-4) (S) -α-cyano-3-phenoxybenzyl (1R, 3R) -3- (2,2-dibromovinyl)-
2,2-dimethylcyclopropanecarboxylate (generic name: deltamethrin) (C-5) (RS) -α-cyano-3-phenoxybenzyl (Z)-(1RS, 3RS) -3- (2-chloro-
(3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate (generic name: cyhalothrin) (C-6) 4-methyl-2,3,5,6-tetrafluorobenzyl-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate (generic name: tefluthrin) (C-7) 2- (4-ethoxyphenyl) -2- Methylpropyl 3-phenoxybenzyl ether (generic name:
Etofenblox) (C-8) (RS) -α-cyano-4-fluoro-3-
Phenoxybenzyl (1RS, 3RS)-(1RS, 3
SR) -3- (2,2-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (generic name: cyfluthrin) (C-9) (RS) -α-cyano-3-phenoxybenzyl 2,2 3,3-tetramethylcyclopropanecarboxylate (generic name: fenpropatrin) (C-10) (RS) -α-cyano-3-phenoxybenzyl (S) -2- (4-difluoromethoxyphenyl) -3 -Methylbutyrate (generic name: flucitrinate) (C-11) (RS) -α-cyano-3-phenoxybenzyl N- (2-chloro-α, α, α-trifluoro-p-tolyl)- D-valinate (generic name: fluvalinate) (C-12) (RS) -α-cyano-3, phenoxybenzyl (RS) -2,2-dichloro-1- (4-ethoxyphenyi) ) Cyclopropanecarboxylate (common name: cycloprothrin Trinh)

(D) Nitro compound (D-1) 1- (6-chloro-3-pyridylmethyl)-
N-nitro-imidazolidine-2-ylideneamine (generic name: imidacloprid) (D-2) 1- [N- (6-chloro-3-pyridylmethyl) -N-ethylamino] -1-methylamino-2, Nitroethylene (European publication No. 302389) (D-3) 1- (6-Chloro-3-pyridylmethyl)-
2- (1-Nitro-2-allylthioethylidene) imidazolidine (European publication No. 433784) (D-4) 1- (6-Chloro-3-pyridylmethyl)-
3-Methyl-2-nitroguanidine (Europe Open N
o.375907) (D-5) 1- (6-chloro-3-pyridylmethyl)-
3,3-dimethyl-2-nitroguanidine (Europe Publication No. 375907)

(E) Benzoylurea compound (E-1) 1- (4-chlorophenyl) -3- (2,6
-Difluorobenzoyl) urea (generic name: diflubenzuron) (E-2) 1- [3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] -3- (2 , 6-Difluorobenzoyl) urea (generic name: chlorofluazuron) (E-3) 1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl)
Urea (generic name: teflubenzuron) (E-4) 1- (2-chlorobenzoyl) -3- (4-
(Trifluoromethoxyphenyl) urea (generic name: triflumuron) (E-5) 1- (2-fluoro-4- (2-chloro-4)
-Trifluoromethylphenoxy) phenyl) -3-
(2,6-difluorobenzoyl) urea (generic name: flufenoxuron) (E-6) 1- (3,5-dichloro-4- (1,1,1)
2,2-tetrafluoroethyl) phenyl) -3-
(2,6-difluorobenzoyl) urea (E-7) 1- (2-fluoro-4- (2-chloro-
1,1,2-trifluoroethylthio) phenyl) -3
-(2,6-difluorobenzoyl) urea

(F) Nereistoxin derivative (F-1) S, S'-2-dimethylaminotrimethylenebis (thiocarbamate) (general name: cartap) (F-2) N, N-dimethyl-1, 2,3-trithian-5-ylamine (generic name: thiocyclam) (F-3) S'-2-dimethylaminotrimethylene di (benzenethiosulfonate) (generic name: bensultap)

(G) Hydrazine compounds (G-1) N'-t-butyl-N'-3 ',-5'-dimethylbenzoyl-N-4-ethylphenylcarbohydrazide (Europe Publication No. 236618) ( G-2) N'-t-butyl-N'-3,5-dimethylbenzoyl-N-benzo [b] thiophen-2-carbohydrazide (European publication No. 483647) (G-3) N'-t- Butyl-N'-3,5-dimethylbenzoyl-N-4,5,6,7-tetrahydrobenzo [b] thiophen-2-carbohydrazide (European publication No. 483647) (G-4) N'-t- Butyl-N'-3,5-dimethylbenzoyl-N-5,6-dihydro-4H-cyclopenta [b] thiophen-2-carbohydrazide (Europe Publication No. 48 3647)

(H) Heterocyclic compound (H-1) 2-tert-butylimino-3-isopropyl-5-phenylperhydro-1,3,5-thiadiazin-4-one (generic name: buprofezin) (H -2) (4RS, 5RS) -5- (4-chlorophenyl) -N-cyclohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide (generic name: hexthiazox) (H-3) 2 -T-butyl-5- (4-t-butylbenzylthio) -4-chloro-3 (2H) -pyridazinone (generic name: pyridaben) (H-4) t-butyl 4-[(1,3-dimethyl -5
-Phenoxypyrazol-4-yl) methyleneaminooxymethyl] benzoate (generic name: fenpyroximate) (H-5) diisopropyl 1,3-dithiolan-2-ylidene-malonate (generic name: isoprothiolane) (H-6) 5- Methyl-1,2,4-triazolo [3,
4-b] Benthiazole (generic name: tricyclazole) (H-7) 1,2,5,6-tetrahydropyrrolo [3
(2,1-ij) quinolin-4-one (generic name: pyroquilon) (H-8) 6- (3,5-dichloro-o-tolyl) pyridazin-3 (2H) -one (generic name: diclomedine) ( H-9) 3-allyloxy-1,2-benzisothiazole-1,1-dioxide (generic name: probenazole) (H-10) (Z) -2'-methylacetophenone-
4,6-dimethylpyrimidin-2-ylhydrazone (generic name: ferimzone)

(I) Phenyl compound (I-1) N-methylbis (2,4-xylyliminomethyl) amine (general name: amitraz) (I-2) N '-(4-chloro-o-tolyl) ) -N, N
-Dimethylformamidine (generic name: chlordimeform)

(J) Silane-based compound (J-1) (4-ethoxyphenyl)-[3- (4-fluoro-3-phenoxyphenyl) propyl] (dimethyl) silane (general names: silafluofen, Heo-49)
8)

(K) Juvenile hormone-like compound (K-1) Isopropyl (E, E)-(RS) -11
Methoxy-3,7,11-trimethyldoteca-2,4-
Dienoate (generic name: methoprene)

(L) Organochlorine Compound (L-1) 2,2,2-Trichloro-1,1-bis (4
-Chlorophenyl) ethanol (generic name: dicofol) (L-2) 4-chlorophenyl-2,4,5-trichlorophenylsulfone (generic name: tetradiphone) (L-3) 4,5,6,7-tetrachlorophthali Do (generic name: Husalide)

(M) Organometallic compound (M-1) bis [tris (2-methyl-2-phenylpropyl) tin] oxide (generic name: fenbutatin oxide)

(N) Anilide compound (N-1) α, α, α-trifluoro-3'-isopropoxy-o-toluanilide (generic name: flutranyl) (N-2) 3'-isopropoxy-o -Toluanilide (generic name: mepronil) (N-3) 1- (4-chlorobenzyl) -1-cyclopentyl-3-phenylurea (generic name: pencyclone)

(O) Antibiotics (O-1) Validamycin A (generic name: validamycin) (O-2) Kasugamycin hydrochloride (generic name: kasugamycin) A hydrazone compound represented by the general formula (I) or a salt thereof Is a novel compound and can be produced, for example, by the following method.

Method (1)

Embedded image (In the formula, X, Y, R ¹ and R ² are as described above.)

Method (2)

Embedded image (In the formula, X, Y, R ³ , R ⁴ and R ⁵ are as described above.)

Method (3)

Embedded image (In the formula, X, Y, R ³ , R ⁴ and R ⁵ are as described above.)

Method (4)

Embedded image (Where X, Y, R ¹ and R ² are as described above, and
l is a halogen atom. ) In addition, the general formula (II)
Can be produced, for example, by the following method.

Method (5)

Embedded image (In the formula, X and Y are as described above.)

Method (6)

Embedded image (In the formula, X, Y and Hal are as described above.)

Method (7)

Embedded image (In the formula, X, Y and Hal are as described above.)

Method (8)

Embedded image (In the formula, X, Y and Hal are as described above, and Ph is phenyl.)

Method (9)

Embedded image (In the formula, X, Y and Ph are as described above.)

Method (10)

Embedded image (In the formula, X and Y are as described above.) The compound represented by the general formula (III) can be produced, for example, by the following method.

[0034] The compound represented by the general formula (IV) can be produced, for example, by the following method.

Method (12)

Embedded image (In the formula, X, Y and R ³ are as described above.) Among the compounds represented by the general formula (V), those in which R ³ is an alkyl group are included in the general formula (I) and described above. The compound represented by the general formula (V), which can be produced by the method (1) and in which R ³ is a hydrogen atom, can be produced according to the aforementioned method (1).

The reactions of the above methods 1 and 11 are usually carried out in the presence of a solvent, if necessary, in the presence of an acid catalyst, and the reaction temperature is usually -20 to + 200 ° C, preferably -10 to + 200 ° C.
The reaction time is usually 0.1 to 150 hours. Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran and dioxane; alcohols such as ethylene glycol, glycerin, methanol and ethanol; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- 2-
Aprotic polar solvents such as pyrrolidone, dimethylsulfoxide and sulfolane; aromatic hydrocarbons such as benzene, toluene and chlorobenzene; halogenated hydrocarbons such as methylene chloride and chloroform; pentane;
Aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; pyridines such as pyridine and picoline; acetic acid; water; Good. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid; formic acid, acetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, p
Organic acids such as toluenesulfonic acid; acid addition salts of amines such as pyridine hydrochloride and triethylamine hydrochloride.

The reaction of the above method 2 is carried out in the presence of a solvent and / or an acid catalyst, if necessary.
The reaction temperature is 200 ° C., preferably 50 to 150 ° C., and the reaction time is usually 0.1 to 100 hours. Examples of the solvent include ethers, alcohols, aprotic polar solvents, aromatic hydrocarbons, halogenated hydrocarbons and water as used in the above methods 1 and 11, and nitriles such as acetonitrile. These solvents may be used in combination. Examples of the acid catalyst include those similar to those used in the above methods 1 and 11.

The reaction of the above method 3 is carried out in the presence of a solvent if necessary, the reaction temperature is usually -20 to + 200 ° C, preferably 0 to 100 ° C, and the reaction time is usually 0.1 to 100 ° C.
100 hours. Examples of the solvent include aromatic hydrocarbons, pyridines, halogenated hydrocarbons, aliphatic hydrocarbons, water and the like as used in the above methods 1 and 11, and these solvents may be used in combination. You may. The reaction of the above method 4 is usually carried out in the presence of a solvent, if necessary, in the presence of an acid binder, and the reaction temperature is usually -20 to +
The temperature is 200 ° C, preferably 0 to 150 ° C, and the reaction time is usually 0.1 to 100 hours. Examples of the solvent include ethers, aprotic polar solvents, aromatic hydrocarbons, halogenated hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and pyridine as used in the above methods 1 and 11. , Water, and inert organic solvents such as nitriles such as acetonitrile, and these solvents may be used in combination. Examples of the acid binder include tertiary alkylamines such as triethylamine, alkali metal carbonates such as sodium carbonate, and pyridine.

The reaction of the above method 5 is a usual Friedel-Crafts reaction, which is carried out in the presence of a solvent and a catalyst,
The reaction temperature is -20 to + 200 ° C, preferably -10 to +
100 ° C., and the reaction time is 0.1 to 100 hours. Examples of the solvent include carbon disulfide, halogenated hydrocarbons used in the above methods 1 and 11, nitrobenzene, and the like. Examples of the catalyst include Lewis acids such as aluminum chloride, lead chloride, ferrous chloride, ferric chloride, titanium tetrachloride, tin chloride, zinc chloride and polyphosphoric acid.

The reactions of the above methods 6 and 7 are ordinary Grignard reactions and are carried out in the presence of a solvent, and the reaction temperature is -20 to + 200 ° C, preferably -10 to + 100 ° C.
And the reaction time is 0.1 to 100 hours. Examples of the solvent include ethers as used in the above methods 1 and 11.

The first-stage reaction of the above methods 8 and 9 is a usual Wittig reaction, which is carried out in the presence of a base and a solvent, at a reaction temperature of -20 to + 200 ° C., preferably -1.
0 to + 150 ° C, and the reaction time is 0.1 to 100 hours. Examples of the base include an alkali (earth) metal hydroxide, carbonate, acetate, and an organometallic compound such as butyllithium. Examples of the solvent include hydrocarbons, ethers, alcohols, aprotic polar solvents, aromatic hydrocarbons, halogenated aromatic hydrocarbons, and halogenated hydrocarbons as used in the above methods 1 and 11. And water, and these solvents may be used as a mixture.

The second stage reaction of the above methods 8 and 9 is a usual halogenation reaction, wherein halogen is present in the presence of a peroxide or under irradiation of light (the halogen is preferably bromine or chlorine). ). The reaction temperature is -20 to
+ 200 ° C, desirably -10 to + 100 ° C, and the reaction time is 0.1 to 100 hours. As the solvent, hydrocarbons and halogenated hydrocarbons are preferably used, but the solvents of the above methods 1 and 11 can also be used.

The third stage reaction of the above methods 8 and 9 is a usual dehalogenation reaction, which is carried out with a dehalogenating agent in the presence of a solvent. Examples of the dehalogenating agent include alkali metals and their alcoholates and hydroxides. The reaction temperature is -20 to + 200 ° C, preferably -10.
To + 150 ° C., and the reaction time is 0.1 to 100 hours. The same solvent as that used in the first-stage reaction can be used as the solvent.

The fourth stage reaction of the above methods 8 and 9 is a usual oxidation reaction, which is oxidized using a mercury (II) salt or the like in the presence of an acid catalyst. Reaction temperature is -20 to + 200 ° C,
Desirably, it is −10 to + 150 ° C., and the reaction time is 0.1.
1 to 100 hours. As the solvent, acetic acid and the same solvents as those used in the first-stage reaction can be used, and these solvents may be mixed and used. Examples of the acid catalyst include inorganic acids such as sulfuric acid and nitric acid, and organic acids such as acetic acid and trifluoroacetic acid. The reaction of the above method 10 is a usual oxidation reaction and is carried out in the presence of a solvent and an oxidizing agent. The reaction temperature is -20 to + 200 ° C, preferably -10 to +1
50 ° C. and the reaction time is 0.1 to 100 hours.
Examples of the oxidizing agent include chromium (VI) salt, lead tetraacetate, nitric acid, dimethyl sulfoxide and the like. As the solvent,
Water and acetic acid are mainly used, and hydrocarbons, halogenated aromatic hydrocarbons, aprotic polar solvents, aromatic hydrocarbons and halogenated hydrocarbons as used in the above methods 1 and 11 are used. And these solvents may be used as a mixture.

The reaction of the above method 12 is carried out in the presence of a solvent, if necessary. The reaction temperature is usually 0 to 250 ° C, preferably 10 to 180 ° C, and the reaction time is 0.1 to 10 ° C.
0 hours. As the solvent, for example, the above methods 1 and 11
And aromatic hydrocarbons, halogenated hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and the like, and these solvents may be used as a mixture. Specific synthesis examples of the compound represented by the general formula (I) will be described.

Synthesis Example 1 Synthesis of [4'-fluoro-2- (4-trifluoromethylphenyl) acetophenone] N '-[1- (dimethylamino) ethylidene] hydrazone (Compound No. 13) 8.9 g of fluorobenzaldehyde (72 m
mol), (4-trifluoromethylbenzyl) triphenylphosphonium chloride 32 g (72 mmol)
Is dissolved in 300 ml of methylene chloride and 280 ml of 3N sodium hydroxide (0.84
mmol) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. After completion of the reaction, liquid separation was performed, and the organic layer was washed twice with water. After drying over anhydrous sodium sulfate, the solvent was distilled off. The residue was purified by silica gel column chromatography (developing solvent: n, hexane) to obtain 12.4 g of 4-fluoro-4'-trifluoromethylstilbene. (2) 12.4 g (47 mmol) of 4-fluoro-4'-trifluoromethylstilbene in 80 ml of chloroform
l) was dissolved in a solution of 2.4 ml (47 mmol) of bromine in 20 m at 40 ° C. while irradiating with a 160 W mercury lamp.
of chloroform solution was added dropwise, and stirring was continued for 30 minutes. After completion of the reaction, the solvent was distilled off to obtain a yellow oily substance. This was dissolved in 100 ml of ethanol without purification, and 12.3 g of potassium hydroxide was added to 45 ml of water while heating under reflux.
An aqueous solution in which was dissolved was added dropwise. After the completion of the dropwise addition, heating and reflux were continued for 3 hours. After completion of the reaction, ethanol was distilled off, water was added to the residue, and the mixture was extracted with ether. After drying over anhydrous sodium sulfate, the solvent was distilled off to obtain 12.2 g of 4-fluoro-4'-trifluoromethyltran as a yellow solid. This was used for the next reaction without purification. (3) 60 ml of water and 60 m of acetic acid were added to 12.2 g (46 mmol) of 4-fluoro-4'-trifluoromethyltran.
1, 40 ml of sulfuric acid, 13.6 g of mercuric sulfate (46 mm
ol) and heated and stirred at 90 ° C. for 3.5 hours. After completion of the reaction, water was added, the mixture was extracted with ether, dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solvent = ethyl acetate: n-hexane = 1: 10). 5.1 g of 4'-fluoro-2- (4-trifluoromethylphenyl) acetophenone having a melting point of 87-89 ° C was obtained. (4) 5.1 g of 4'-fluoro-2- (4-trifluoromethylphenyl) acetophenone (18.1 mmol)
l) was dissolved in 100 ml of ethanol, 8.8 ml (181 mmol) of hydrazine monohydrate was added thereto, and these were heated under reflux for 2 hours. After completion of the reaction, ethanol was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with dichloromethane. After drying over anhydrous sodium sulfate and evaporating the solvent, [4'-fluoro-2- (4-trifluoromethylphenyl) acetophenone] hydrazone was obtained as a yellow oil. (5) [4'-fluoro-2 obtained in the above step (4)
-(4-Trifluoromethylphenyl) acetophenone] hydrazone, and 3.13 g (23.5 mmol) of N, N-dimethylacetamidodimethylacetal were added.
Heated at 20 ° C. for 2 hours. After completion of the reaction, the residue was subjected to silica gel column chromatography (developing solvent = ethyl acetate:
n-hexane = 1: 19) to give a melting point of 86-88.
3.10 g of the target product (compound No. 13) at ℃ was obtained.

In the present invention, the mixing ratio of at least one hydrazone compound represented by the above general formula (I) or a salt thereof to another active ingredient is from 1: 100 to 10:10.
0: 1, preferably 1:50 to 50: 1. The pesticidal composition of the present invention is, as in the case of conventional agricultural chemical formulations, emulsions, powders, granules, wettable powders, wettable powders, wettable powders, suspensions, liquids, aerosols, together with pesticide adjuvants. It can be formulated in various forms such as a paste. The mixing ratio of these components is usually 0.1 to 90 parts by weight of the active ingredient, preferably 0.1 to 90 parts by weight.
For 5 to 90 parts by weight, more preferably 0.5 to 80 parts by weight, 10 to 99.9 parts by weight, preferably 10 to 99.5 parts by weight, more preferably 20 to 99.
5 parts by weight. In the actual use of these preparations, they can be used as they are or diluted to a predetermined concentration with a diluent such as water.

[0048] Examples of the pesticide auxiliary herein include a carrier, an emulsifier, a suspending agent, a dispersing agent, a spreading agent, a penetrating agent, a wetting agent, a thickener, an antifoaming agent, a stabilizer, and an antifreezing agent. It may be added as needed. The carrier is divided into a solid carrier and a liquid carrier, and as the solid carrier, starch, activated carbon, soybean flour, wheat flour, wood flour, fish flour, animal and plant powders such as milk powder, talc, kaolin, bentonite, calcium carbonate, zeolite, Diatomaceous earth, white carbon, clay,
Mineral powders such as alumina, sulfur powder, anhydrous sodium sulfate, etc., and liquid carriers include water, alcohols such as methyl alcohol and ethylene glycol, ketones such as acetone, methyl ethyl ketone and N-methyl-2-pyrrolidone. , Dioxane, ethers such as tetrahydrofuran, kerosene, aliphatic hydrocarbons such as kerosene, xylene, trimethylbenzene, aromatic hydrocarbons such as tetramethylbenzene, cyclohexane, solvent naphtha, halogenated hydrocarbons such as chloroform and chlorobenzene , Acid amides such as dimethylformamide, esters such as ethyl acetate and glycerin ester of fatty acid, nitriles such as acetonitrile, sulfur-containing compounds such as dimethyl sulfoxide, soybean oil, corn oil What vegetable oils and the like.

The pest control composition of the present invention may be prepared by mixing active ingredients, or may be prepared by mixing each active ingredient in advance. The pest controlling composition of the present invention has a controlling effect on insects, mites, nematodes and various diseases which are harmful to agricultural and horticultural activities. In particular, planthoppers occurring in paddy fields, Hemiptera pests such as leafhoppers and lepidopteran pests such as squid and moss, or important diseases of rice such as rice blast and rice sheath blight, aphids occurring in the field, etc. It is effective in controlling Hemiptera pests and lepidopteran pests such as diamondback moths and common cutworm.

When the pest control composition of the present invention is applied, the hydrazone compound represented by the general formula (I) or a salt thereof is generally used in an amount of 1 to 100,000 ppm, preferably 1 to 100 ppm.
~ 50,000 ppm, more preferably 10-20,
000 ppm, the other active ingredients are generally from 1 to 100,00
It is carried out at a concentration of each active ingredient of 0 ppm, preferably 1 to 50,000 ppm, more preferably 10 to 20,000 ppm. The concentration of these active ingredients may deviate from these ranges depending on the form of the preparation, the method of application, the purpose, the time, the place, the occurrence of pests, and the like. For example, in the case of aquatic pests, even if a chemical solution having the above-mentioned concentration range is sprayed at the place of occurrence, control can be carried out. The application rate per unit area is preferably about 1 to 50,000 per ha of the hydrazone compound represented by the general formula (I) or a salt thereof as an active ingredient compound.
g, preferably 10 to 10,000 g, and the other active ingredient is about 1 to 50,000 g, preferably 10 to 1 g.
000 g are used. However, in special cases, it is possible to deviate from these ranges. In addition, the application is usually carried out in a generally practiced manner, that is, spraying (eg, spraying, spraying, misting, atomizing, granulation, surface application, etc.), soil application (mixing, irrigation, etc.), surface application (application) , Dressing, coating, etc.), immersion poison bait and the like. Further, it is also possible to feed the livestock with the above-mentioned active ingredient by mixing it with livestock to control the development and growth of harmful insects, particularly harmful insects, in their excrement. It can also be applied by the so-called ultra low volume method. In this method, it is possible to contain 100% of the active ingredient.

[0051]

EXAMPLES Examples of the formulation of the pest control composition of the present invention will be described. However, the types, blending ratios, dosage forms, etc. of the active ingredient compound and the pesticide auxiliary are not limited to the described examples.

Formulation Example 1 (a) Compound No. 12 20 parts by weight (b) Compound D-1 10 parts by weight (c) Kaolin 42 parts by weight (d) Sodium ligninsulfonate 8 parts by weight (e) White carbon 20 parts by weight .

Formulation Example 2 (a) Compound No. 133 parts by weight (b) 1.5 parts by weight of compound H-1 (c) 95.5 parts by weight of talc The above components are uniformly mixed to form a powder.

Formulation Example 3 (A) Compound No. 15 10 parts by weight (b) Compound B-8 50 parts by weight (c) N-methyl-2-pyrrolidone 10 parts by weight (d) polyoxyethylene alkylphenyl ether 10 parts by weight (e) xylene 20 parts by weight Mix and dissolve uniformly to form an emulsion.

Formulation Example 4 (a) 83 parts by weight of kaolin (b) 2 parts by weight of sodium ligninsulfonate (c) 5 parts by weight of polyoxyethylene alkylaryl sulfate (4) 10 parts by weight of finely divided silica A mixture of the above components and , Compound No. 2 and compound D-
And 2 at a weight ratio of 7: 2: 1 to obtain a wettable powder.

Formulation Example 5 (a) Compound No. 14 20 parts by weight (b) 10 parts by weight of compound E-2 (c) 2 parts by weight of oxidized polyalkylphenol phosphatotriethanolamine (d) 0.2 parts by weight of silicone (e) 0.1 parts by weight of xanthan gum ( F) Ethylene glycol 5 parts by weight (g) Water 62.7 parts by weight The above components are uniformly mixed and pulverized to obtain an aqueous suspension.

Formulation Example 6 (a) Compound No. 12 25 parts by weight (b) 50 parts by weight of compound A-8 (c) 43.5 parts by weight of sodium polycarboxylate (d) 10 parts by weight of anhydrous sodium sulfate (e) 0.5 parts by weight of dextrin (f) Alkyl sulfonic acid Sodium 1 part by weight Put each of the above components in a high-speed mixing granulator, and further add
% Water is added and granulated and dried to obtain a wettable powder.

Formulation Example 7 (a) Compound No. 135 parts by weight (b) 5 parts by weight of compound B-4 (c) 33 parts by weight of bentonite (d) 52 parts by weight of kaolin (e) 5 parts by weight of sodium ligninsulfonate Addition, mixing and granulation yield granules.

Formulation Example 8 (a) Compound No. 14 2 parts by weight (b) Compound C-3 0.5 part by weight (c) N-methyl-2-pyrrolidone 2.5 parts by weight (d) Soybean oil 95.0 parts by weight The above components are uniformly mixed and dissolved. And a small amount of spray (ult
ra low volume formula
n).

Formulation Example 9 (A) Compound No. 13 10 parts by weight (b) Compound A-11 10 parts by weight (c) N-methyl-2-pyrrolidone 5 parts by weight (d) polyoxyethylene alkylaryl (aryl) ether 10 parts by weight (e) xylene 65 parts by weight or more Are uniformly mixed to form an emulsion.

Formulation Example 10 (a) Compound No. 15 10 parts by weight (b) Compound G-1 10 parts by weight (c) Corn oil 67 parts by weight (d) Polyoxyethylene hydrogenated castor oil 12 parts by weight (e) Organic bentonite 1 part by weight Grinding gives a suspension.

Formulation Example 11 (A) Compound No. 12 3 parts by weight (b) Compound N-1 2 parts by weight (c) Talc 95 parts by weight The above components are uniformly mixed to obtain a powder.

Formulation Example 12 (a) Compound No. 23 parts by weight (b) 1 part by weight of compound H-6 (c) 96 parts by weight of clay The above components are uniformly mixed to form a powder.

Formulation Example 13 (a) Compound No. 143 parts by weight (b) 0.5 parts by weight of compound J-1 (c) 96.5 parts by weight of talc The above components are uniformly mixed to form a powder.

Formulation Example 14 (a) Compound No. 15 3 parts by weight (b) Compound L-3 2 parts by weight (c) Clay 95 parts by weight The above components are uniformly mixed to form a powder.

Formulation Example 15 (a) Compound No. 12 3 parts by weight (b) Compound O-1 0.3 part by weight (c) Talc 96.7 parts by weight The above components are uniformly mixed to form a powder.

Test Example 1 Insecticidal test of Spodoptera litura Leaf pieces of cabbage were immersed in a chemical solution adjusted to a predetermined concentration for about 10 seconds and air-dried. A wet filter paper was spread on a petri dish having a diameter of 9 cm, and air-dried leaf pieces were placed thereon. There 2-3
Release 10 larvae of the cutworm cutworm, cover and cover 26
It was left in a thermostat with illumination at ℃. On the 4th day after the release, viability was determined. The mortality was calculated by the following formula, and the results in Table 2 were obtained. Death rate (%) = (number of dead insects / number of released insects) x 100

[0068]

[Table 2]

Test Example 2 Insect Insect Test In the same manner as in Test Example 1, except that 2-3 years old Spodoptera litura was replaced with 2-3 years old Japanese moth, and the survival was determined on the third day after release. A test was performed to determine the mortality, and the results in Table 3 were obtained.

[0070]

[Table 3]

Test Example 3 Insecticidal test of the corn beetle Corn leaf leaf was added to a chemical solution adjusted to a predetermined concentration by about 10 %.
Dipped for seconds and air dried. A wet filter paper was spread over an ice cream cup having a diameter of 8 cm, and air-dried leaf pieces were placed thereon. There were released five 2-3-year-old larvae of the larvae of Kobumemeiga, which were capped and left in a 26 ° C. illuminated incubator. After release 2
On the day, life and death were determined, and the mortality was determined in the same manner as in Test Example 1 above, and the results in Table 4 were obtained.

[0072]

[Table 4]

Test Example 4 Rice Planthopper Insecticidal Test Rice seedlings were immersed in a chemical solution adjusted to a predetermined concentration for about 10 seconds, air-dried, and the roots were wrapped with moist absorbent cotton and placed in a test tube. Then, ten larvae of the brown planthopper were released into this, the tube opening was covered with gauze, and the tube was allowed to stand in a 26 ° C. lighted incubator. On the third or fifth day after the release, the survival was determined, and the mortality was determined in the same manner as in Test Example 1 above.
The results of 1 and 5-2 were obtained.

[0074]

[Table 5]

[0075]

[Table 6]

Test Example 5 Peach Aphid Insecticidal Test Eggplant leaving only one true leaf was used as a cup (diameter 8c).
m, height 7 cm), and inoculated with two to three adult female peach aphids, female wingless embryos. Inoculation 2
After a day, the adults were removed and the larvae were counted. The eggplant leaves infested with the larvae were immersed in a chemical solution adjusted to a predetermined concentration for about 10 seconds, air-dried, and allowed to stand in a 26 ° C illuminated thermostat. On the second day after the release, survival was determined, and the mortality was determined by the following formula, and the results in Table 6 were obtained. The withdrawn insects were regarded as dead. Death rate (%) = (number of dead insects / number of treated insects) x 100

[0077]

[Table 7]

Test Example 6 Rice Sheath Blight Prevention Effect Test Rice (cultivar: Koshihikari) was cultivated in a plastic pot having a diameter of 7.5 cm, and when the five-leaf stage was reached, a chemical solution in which each test compound was adjusted to a predetermined concentration was obtained. 20 ml was sprayed using a spray gun. After being kept in a constant temperature room at 22 to 24 ° C. for 24 hours, rice straw in which sheath blight fungus had been cultured was sandwiched between leaf sheath portions and inoculated. After being kept in an inoculation room at a temperature of 28 ° C. and a humidity of 100% for 5 days, the lesion length was examined, and a control index was obtained according to the following evaluation criteria, and the results in Table 7 were obtained. Evaluation Criteria The control effect was determined by visually observing the degree of onset of the test plant at the time of the survey, and the control index was determined in the following five stages. [Control index] [Degree of disease onset] 5: No lesion is observed at all 4: The number of lesions or the lesion length is less than 10% of the untreated section 3: The number of lesions or the lesion length is not treated Less than 40% 2: The number of lesions or lesion length is less than 70% of the untreated section 1: The number of lesions or lesion length is 70% or more of the untreated section

[0079]

[Table 8]

Test Example 7 Test for Rice Blast Preventive Effect A rice (cultivar: Koshihikari) was cultivated in a plastic pot having a diameter of 7.5 cm. When the four leaf stage was reached, 20 ml of a drug solution in which each test compound was adjusted to a predetermined concentration was obtained. Was sprayed using a spray gun. After being kept in a constant temperature room at 22 to 24 ° C. for 24 hours, a spore suspension of the blast fungus was sprayed and inoculated. Five days after the inoculation, the number of lesions was examined, and the control index was determined according to the evaluation criteria of Test Example 6 above, and the results in Table 8 were obtained.

[0081]

[Table 9]

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) A01N 47/24 A01N 37/28 A01N 35/10 CA (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (I) (Wherein X is a hydrogen atom, a halogen atom, an alkyl group optionally substituted with a halogen atom or an alkoxy group optionally substituted with a halogen atom, and Y is a halogen atom, R ¹ is a hydrogen atom or an alkyl group, R ² is an alkylcarbonyl group or an alkoxycarbonyl group, and R ¹ and R ² are ^May form a ＣＲCR ³ NR ⁴ R ⁵ group, wherein R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group) or a salt thereof. And an organic phosphorus compound, a carbamate compound, a pyrethroid compound,
Nitro compounds, benzoyl urea compounds, nereistoxin derivatives, hydrazine compounds, heterocyclic compounds, phenyl compounds, silane compounds, juvenile hormone compounds, organochlorine compounds, organometallic compounds, anilide compounds And a pest control composition comprising, as an active ingredient, at least one compound selected from the group consisting of antibiotics.