JPH07324068A - Hydrazone compound and insecticidal and acaricidal agent containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain the compound represented by a specific formula and exhibiting excellent insecticidal and acaricidal effects. CONSTITUTION:A compound of formula [X is halogen; R<1> is H, halogen, cyano, (substituted) 1-4C alkyl, (substituted) 1-4C alkoxy; R<2> is trifluoromethyl, methyl; R<3>, R<4> are H, (substituted) 1-4C alkylthio, 1-4C alkylthio, 1-4C alkylsulfinyl, alkylsulfonyl, (substituted) 1-5C alkyl, (substituted)phenyl, group of formula II (R<5>, R<6> are H, 1-4C); (n) is 0,1] e.g. N'-[N-methyl-n(S-methyl-1- dimethylcarbamoylthioformimide-N-oxycarbonyl) aminosulfenyl]-N'- ethoxycarbonylhydrazono-4-chloro-4'-(trifluoromethanesulfonyloxy)benzo phenone. the compound is preferably produced by reacting a compound of a formula III and a compound of formula IV with sulfur dichloride in the presence of a base, and further reacting the reaction product.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a hydrazone compound and an insecticidal and acaricidal agent containing the same as an active ingredient.

The present inventors have conducted extensive studies to find an excellent insecticidal and acaricidal agent, and have found that the hydrazone compound represented by the following general formula 3 has excellent insecticidal and acaricidal activity. The present invention has been completed. That is, the present invention provides a compound represented by the general formula

[Chemical 3] [In the formula, X represents a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom, etc.), R ¹ represents a hydrogen atom, or a halogen atom, a cyano group or an alkoxy group having 1 to 3 carbon atoms. 1 carbon atom which may be substituted with
Represents an alkyl group having 4 to 4 or an alkoxy group having 1 to 4 carbon atoms which may be substituted with a halogen atom. R ² represents a trifluoromethyl group or a methyl group, R ³ and R ⁴ are the same or different and represent a hydrogen atom, or an alkylthio group having 1 to 4 carbon atoms,
Alkylsulfinyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
Or an alkylsulfonyl group having 1 to 5 carbon atoms which may be substituted with a cyano group, or an alkylthio group having 1 to 4 carbon atoms which may be substituted with a cyano group, or Represents a phenyl group which may be substituted with a halogen atom, or has the general formula

[Chemical 4] (In the formula, R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). n represents 0 or 1. ] The hydrazone compound (Hereinafter, it is described as this invention compound.) Shown by these, and the insecticide and acaricide which contain it as an active ingredient are provided.

In the compound of the present invention, represented by R ¹ ,
Examples of the alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, a cyano group or an alkoxy group having 1 to 3 carbon atoms include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec. -Butyl group, tert
-Butyl group, difluoromethyl group, trifluoromethyl group, 1,1,2,2-tetrafluoroethyl group, pentafluoroethyl group, chloromethyl group, 2-chloroethyl group, bromomethyl group, cyanomethyl group, methoxymethyl group, Examples thereof include an ethoxymethyl group and a 2-methoxyethyl group, each of which has a carbon number of 1 to 1 which may be substituted with a halogen atom.
Examples of the alkoxy group of 4 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a 2-chloroethoxy group and a 2-fluoroethoxy group. .
In the compound of the present invention, substituted with an alkylthio group having 1 to 4 carbon atoms, an alkylsulfinyl group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms or a cyano group, which is represented by R ³ and R ^4. Good carbon number 1-5
Examples of the alkyl group include 1- (methylthio) ethyl group, 1- (methylsulfonyl) ethyl group, 1-methyl-1- (methylthio) ethyl group, 1-methyl-1-
(Methylsulfinyl) ethyl group, 1-methyl-1-
(Methylsulfonyl group) ethyl group, 1,1-dimethyl-
Examples thereof include a 3-cyanopropyl group, a methylthiomethyl group, a methyl group, a tert-butyl group and the like, and as the alkylthio group having 1 to 4 carbon atoms which may be substituted with a cyano group,
Examples thereof include a methylthio group and a 2-cyanoethylthio group. Examples of the phenyl group which may be substituted with a halogen atom include a 4-chlorophenyl group and the like. Examples of the group represented by the general formula 2 are: For example, N,
Examples thereof include N-dimethylcarbamoyl group and N, N-diethylcarbamoyl group.

Of the compounds of the present invention, the compound with n = 0 can be produced, for example, by the following production method A. (Production Method A) General Formula 5

[Chemical 5] [In the formula, X, R ¹ and R ² have the same meanings as described above. ] And the compound of the general formula:

[Chemical 6] [In the formula, R ³ and R ⁴ have the same meanings as described above. ]
A method of reacting with a compound represented by the formula (1) and sulfur dichloride in the presence of a base. In the production method A, a solvent is not always necessary, but it is generally preferable to carry out in an inert organic solvent. When a solvent is used, it is generally, for example, benzene, toluene, xylene, chlorobenzene or o-diene. Aromatic hydrocarbons such as chlorobenzene, chloroform, carbon tetrachloride, 1,2-dichloroethane,
Halogenated hydrocarbons such as 1,1,1-trichloroethane, tetrachloroethylene, trichloroethylene, n
-Aliphatic hydrocarbons such as hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane, alcohols such as methanol, ethanol and isopropanol, aprotic polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide Ethers such as tetrahydrofuran, diethyl ether and the like, ketones such as acetone and methyl isobutyl ketone, water and the like or a mixed solvent thereof are used. Examples of the base used include organic bases such as triethylamine, pyridine, 4-N, N-dimethylaminopyridine and N, N-diethylaniline, inorganic bases such as sodium hydroxide, sodium hydride and potassium carbonate, butyl lithium. , Organic metal bases such as lithium diisopropylamide, and the like. The amount of the reaction reagent used in the production method A is usually 1 mol of the compound represented by the general formula:
The ratio is 0.1 to 10 moles, the base is usually 0.1 to 10 moles, and the reaction temperature of the reaction is usually -78 to 10 degrees Celsius.
The range of 0 degree and the reaction time are usually in the range of 5 minutes to 100 hours. After completion of the reaction, the desired compound of the present invention can be isolated by subjecting to ordinary post-treatment such as extraction with an organic solvent and concentration. If necessary, it can be further purified by a method such as chromatography or recrystallization.
In the production method A, a compound represented by the general formula 7 can be obtained by reacting the compound represented by the general formula 6 with sulfur dichloride in the presence of a base.

[Chemical 7] [In the formula, R ³ and R ⁴ have the same meanings as described above. ]
After isolating the compound represented by the formula as an intermediate, it may be reacted with the compound represented by the general formula 5 in the presence of a base.

Of the compounds of the present invention, the compound of n = 1 can be produced, for example, by the following production method B. (Production Method B) The compound represented by the general formula:

[Chemical 8] [In the formula, R ³ and R ⁴ have the same meanings as described above. ] The method of manufacturing by making the compound shown by these, and reacting this compound with the compound shown by General formula 5. A solvent is not always necessary in the production method B,
Generally, it is preferably carried out in an inert organic solvent, and when a solvent is used, it is generally, for example, aromatic hydrocarbon such as benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, chloroform, tetrachloride and the like. Carbon 1,
2-dichloroethane, 1,1,1-trichloroethane,
Halogenated hydrocarbons such as tetrachloroethylene and trichlorethylene, aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane,
An aprotic polar solvent such as N, N-dimethylformamide or dimethylsulfoxide, an ether such as tetrahydrofuran or diethyl ether, a ketone such as acetone or methyl isobutyl ketone, or a mixed solvent thereof is used. The reaction of the compound represented by the general formula 6 with thionyl chloride is preferably carried out in the presence of a base, and examples of the base used include triethylamine, pyridine, 4-N, N-dimethylaminopyridine, N, N.
-Organic bases such as diethylaniline, sodium hydroxide,
Examples thereof include inorganic bases such as sodium hydride and potassium carbonate, and organic metal bases such as butyllithium and lithium diisopropylamide. The reaction between the compound represented by the general formula (8) and the compound represented by the general formula (5) is usually desirably carried out in the presence of a base.
For example, organic bases such as triethylamine, pyridine, 4-N, N-dimethylaminopyridine, N, N-diethylaniline, inorganic bases such as sodium hydroxide, sodium hydride and potassium carbonate, butyllithium, lithium diisopropylamide and the like. Examples thereof include organic metal bases. The amount of the reaction reagent used in the production method B is usually 0.1 to 100 mol of thionyl chloride with respect to 1 mol of the compound represented by the general formula, and the compound represented by the general formula 5 is usually 0. 0.1 to 100 mol ratio, the base is usually 0.1 to
The reaction temperature of the reaction is usually −78 to 100 ° C., and the reaction time is usually 5 minutes to 100 hours. After completion of the reaction, the desired compound of the present invention can be isolated by subjecting to ordinary post-treatment such as extraction with an organic solvent and concentration. If necessary, it can be further purified by a method such as chromatography or recrystallization. Further, the compound represented by the general formula 8 may be isolated from the reaction mixture, but it can also be used as it is in the reaction mixture without isolation for the reaction with the compound represented by the following general formula 5.

The compound represented by the general formula 5 used as a raw material in the production method A can be produced, for example, by the production method a shown below. (Production method a) Formula 9

[Chemical 9] [In the formula, X and R ² have the same meanings as described above. ] And the compound represented by the general formula:

[Chemical 10] [Wherein X and R ¹ have the same meanings as described above, Z
Represents a chlorine atom, a bromine atom, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group or a —OCOR ¹ group. ] The method of making it react with the compound shown by these. In the manufacturing method,
Although a solvent is not always necessary, it is generally preferable to carry out in an inert organic solvent. Needless to say, when a solvent is used, it may be properly used depending on the type of Z, but generally, for example, benzene, toluene, xylene. , Chlorobenzene, aromatic hydrocarbons such as o-dichlorobenzene, pyridines such as pyridine and picoline, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, tetrachloroethylene, halogenated trichloroethylene, etc. Hydrocarbons, aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane, alcohols such as methanol, ethanol and isopropanol, N, N-dimethylformamide,
An aprotic polar solvent such as dimethyl sulfoxide, ethers such as tetrahydrofuran and diethyl ether, ketones such as acetone and methyl isobutyl ketone, water and the like, or a mixed solvent thereof is used. In the production method, when Z is a chlorine atom, a bromine atom, a group represented by -OCOR ¹ or an alkoxy group having 1 to 4 carbon atoms in the compound of the general formula 10, the reaction is carried out in the presence of a base. Good. Examples of the base used include organic bases such as triethylamine, pyridine, 4-N, N-dimethylaminopyridine and N, N-diethylalinine, inorganic bases such as sodium hydroxide, sodium hydride and potassium carbonate, and butyl. Examples thereof include organic metal bases such as lithium and lithium diisopropylamide. When Z represents a hydroxyl group in the compound of general formula 7, the reaction may be carried out in the presence of a condensing agent. Examples of the condensing agent used include organic acid chlorides such as tosyl chloride and pivaloyl chloride, Lewis acids such as titanium tetrachloride and dehydrating agents such as dicyclohexylcarbodiimide, phosphorus pentoxide and polyphosphoric acid. The amount of the reaction reagent used in the production method is usually 1 to 1 with respect to 1 mol of the compound represented by the general formula:
The amount of the compound represented by the general formula 10 is usually 1 to 100 mol, and the reaction temperature of the reaction is
Usually in the range of -20 to 200 ° C, the reaction time is usually 5 minutes to
It is in the range of 100 hours. After completion of the reaction, the compound represented by the general formula 3 can be isolated by performing usual post-treatments such as extraction with an organic solvent and concentration.

The compound represented by the general formula 9 used as the starting material compound in the production method a is, for example, US Pat.
It can be produced by the method described in 4,344,893. In the compound of the present invention, C = of the hydrazone moiety
There are four geometric isomers in total due to the configuration of the N double bond, and two due to the configuration of the alkylideneaminooxy group moiety with respect to the C═N double bond. 4 geometric isomers (E and Z)
And mixtures thereof.

Examples of harmful insects and harmful mites which the compound of the present invention has a controlling effect on include the following. Hemiptera small brown planthopper (Laodelphax striatellus), brown planthopper (Nilaparvatalugens), Sejirounka (Sogatel
l furcifera ), such as planthoppers, leafhoppers ( N)
leafhoppers such as ephotettix cincticeps ), green leafhopper ( Nephotettixvirescens ), aphids, stink bugs, whiteflies, scale insects,
Coleoptera, Pyllidae and other pests of the order Lepidoptera, Chilo suppressalis , Cobnomaiga ( Cn
aphalocrocis medinalis ), European corn borer ( Ostrinia nubilalis ), Shibatga ( Parpediasia )
teterrella ), cotton bollworm ( Notarcha nubilali )
s ), Nostella medusa ( Plodia interpunctella)
) Etc., Spodoptera litu
ra ), armyworm ( Pseudalitia separata ), armyworm ( Mamestra brassicae ), tamanaga ( Agotis ipsil )
on ), Turkish Prussia, Heliotis, Hercovelpa and other moths, Pieris rapae cru
civora ) and other butterflies, such as Adoxophyes, Grapholita molesa , and codling moths ( Cydia pomonella ), such as mosquitoes ( Carposia niponensis ), such as Rinettia, and genus Remantoria, Euprotitis Plutella x
ylostella ) and other stag beetles, the cotton bollworm ( Pectinop)
hora gossipiella) Kibaga such as, the United States white Arctiidae (Hyphantria cunea) Hidoriga such as clothes moth (Tinea
translucens ), Koiga ( Tineola bisselliela ), etc., etc., Diptera pests Culex pipiens pallens , Culex tritaeniorhynchus , Culex tritaeniorhynchus, etc., Ae
Ades, such as des aegypti , Aedes albopictus , An
Anopheles genus, such as opheles sinensis , chironomids,
Housefly ( Musca domestica ), Housefly ( Muscin
a stabulans ), such as house flies, blow flies, flesh flies, house flies, sand flies ( Delia platura ),
Onion fly ( Delia antigua ) and other fruit flies, fruit flies, fruit flies, butterfly flies, gnats,
Western Cone Rootworm ( Diabrotica virgifer)
a) Southern corn rootworm ( Diabrotica undecimp
unctata ) and other corn room worms, Rana buoy ( Anomala cuprea ), Scutellaria baicalensis ( Anomala rufocu )
prea ) and other scarabs , Maize Weevil ( Sitoph
ilus zeamais ), rice weevil ( Lissorhoptrus or
yzophilus), alfalfa weevil ( Hypera p
astica ), Adzuki bean weevil ( Calosobruchys chienensi)
s) weevil such as, chai loco Meno garbage Shi damascene (T
enebrio molitor ), Tricium cas ( Tribolium cas)
Taneum ) and other beetles
ophora femoralis ), Phyllotreta
striolata ), Colorado potato beetle ( Lepitinotarsa decem)
lineata ) and other beetle beetles, beetles, Epilachna vigintioctopunctata ) and other epilacunas, flat beetles, long beetles, long beetles, longhorn beetles, and green leaf beetles ( Paed)
erus fuscipes ), etc. Orthoptera pests Blattella germanica ), Black cockroaches ( Periplaneta fuliginosa ), American cockroaches ( Pe
roplaneta americana ), Black-tailed Cockroach ( Periplan)
eta brunnca ), North American cockroach ( Blatta orientali)
s) Thysanoptera South kilometers thrips such as (Thrips palmi), green onion thrips (Thrips tabaci), Hana thrips (Thrips hawai
Iensis) etc. Hymenoptera ants, wasps, Arigatabachi acids, sawfly, etc. Orthoptera pests eclipse such Kaburahabachi, grasshoppers, etc. Siphonaptera pests human flea (Purex irritans), etc. Anoplura body lice, crab louse (Phthirus pubis), etc. Isoptera pests Yamato termites ( Reticulitermes spentus ), house termites ( Coptermes formosanus ) and other mites Tetranychus uriticae , Tetranychus cinnabarinus , Tetranychus cinnabarinus , Tetr
anychus kazawai), citrus red mite (Panonychus citr
i ), apple spider mite (Ponychus ulmi ), spider mites such as Oligonicas, citrus rust mite ( Aculops peleka)
ssi), Fushidani such as Chanosabidani (Calacarus carinatus), Chanohokoridani (Polyphaqotarsonemu
s latus ) and other dust mites, house dust mites, mosquito mites, ticks such as Boophilus microplus , spider mites, house dust mites such as Pyroglyphidae, claw mites, and black mites, and further resistance to existing insecticides and acaricides It is also effective against pests with developed power.

When the compound of the present invention is used as an active ingredient of insecticides and acaricides, it may be used as it is without adding any other ingredients, but it is usually a solid carrier, a liquid carrier, a gaseous carrier or a bait. Formulated in oils, emulsions, wettable powders, flowables, granules, aerosols, fumes (fogging, etc.), poison baits, etc. To use. Moreover, a stabilizer is added if necessary. These formulations usually contain the compound of the present invention as an active ingredient in an amount of 0.01% to 95% by weight. Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talc, ceramics, other inorganic minerals (serisite,
Quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers (ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.), and other fine powders or granules can be used. , Alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (hexane, cyclohexane,
Kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylacetamide, etc.) ), Halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethylsulfoxide, soybean oil, vegetable oils such as cottonseed oil, and the like, and examples of the gaseous carrier, that is, propellant include freon gas, butane gas, LPG (liquefaction). (Natural gas), dimethyl ether, carbon dioxide and the like. Examples of the surfactant include alkyl sulfate ester salts, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenated products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. Can be mentioned. Examples of formulation aids such as sticking agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol, Polyvinyl chloridone, polyacrylic acid, etc.) and the like, and examples of the stabilizer include BHT (2,6-di-tert-butyl-4-methylphenol) and BHA (2-tert-butyl-4-methoxy). Phenol and 3-tert-butyl-4-
Mixtures with methoxyphenol), alkali metal carbonates such as sodium carbonate and potassium carbonate, metal oxides such as calcium oxide, tertiary amines such as tributylamine and N, N-dimethylaniline, fatty acid salts such as sodium acetate, Examples thereof include sulfates such as calcium sulfate, urea, ethylene glycol, vegetable oils, mineral oils and surfactants.
Examples of poison bait bases include bait ingredients such as cereal flour, vegetable oil, sugar, and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, and pepper powder. Food inhibitors,
Attractive flavors such as cheese flavors and onion flavors can be used.

The thus obtained preparation is used as it is or after diluted with water or the like. Also other pesticides,
It can be used simultaneously with or without mixing with nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers, animal feeds and the like. Examples of the insecticides, nematicides and acaricides used include fenitrothion [O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate, phenthion [O, O-dimethyl-O- ( 3-Methyl-4- (methylthio) phenyl) phosphorothioate, diazinone, [O, O-diethyl-O-2-isopropyl-6-
Methylpyrimidin-4-ylphosphorothioate], chlorpyrifos [O, O-diethyl-3,5,6-trichloro-2-pyridylphosphorothioate], acephate [O, S-dimethylacetylphosphoramidothioate], methidathion [S-2 , 3-Dihydro-5-methoxy-2-oxo-1,3,4-thiadiazole-3-
Ilmethyl-O, O-dimethyl phosphorodithioate], disulfoton [O, O-diethyl-S-2-ethylthioethyl phosphorothioate], DDVP [2,2
-Dichlorovinyl dimethyl phosphate], sulphophos [O-ethyl-O-4- (methylthio) phenyl-
S-propyl phosphorodithioate], cyanophos [O
-4-Cyanophenyl-O, O-dimethyl phosphorothioate], dioxabenzophos [2-methoxy-4H-
1,3,2-benzodioxaphosphinin-2-sulfide], dimethoate [O, O-dimethyl-S (N-methylcarbamoylmethyl) dithiophosphate], fentoate [ethyl-2-dimethoxyphosphinothioylthio] (Phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl-2,2,2-trichloro-1-hydroxyethylphosphonate], azinephosmethyl [3,4-dihydro-4-oxo]. -1, 2, 3
-Benzotriazin-3-ylmethyl-O, O-dimethylphosphorothioate], monocrotophos [dimethyl-
(E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate], ethion [O, O, O ′, O′-tetraethyl-S, S′-methylenebis (phosphorodithioate)] and other organic phosphorus compounds Compound, BPMC [2-sec
-Butylphenylmethylcarbamate], benfuracarb [ethyl-N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl)]
Aminothio] -N-isopropyl-β-alaninate], propoxur [2-isopropoxyphenyl-N
-Methyl carbamate], carbosulfan [2,3-
Dihydro-2,2-dimethyl-7-benzo [b] furanyl-N-dibutylaminothio-N-methylcarbamate], carbaryl [1-naphthyl-N-methylcarbamate], mesomil [S-methyl-N-[( Methylcarbamoyl) oxy] thioacetimidate), ethiophenecarb [2- (ethylthiomethyl) phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde-O-methylcarbamoyloxime], oxamyl [N, Carbamate compounds such as N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide] and phenothiocarb [S- (4-phenoxybutyl) -N, N-dimethylthiocarbamate], etofenprox [2- (4
-Ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether], fenvalerate [(R
S) -α-Cyano-3-phenoxybenzyl ether-
(RS) -2- (4-chlorophenyl) -3-methylbutyrate], phenpropatorin [(RS) -α-cyano-3-phenoxybenzyl-2,2,3,3-tetramethylcyclopropanecarboxylate ], Cypermethrin [(RS) -α-cyano-3-phenoxybenzyl (1RS, 3RS)-(1RS, 3RS) -3- (2
2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl- (1RS, 3RS)-(1RS, 3RS)-
3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], cyhalothrin [(R
S) -α-Cyano-3-foxybenzyl- (Z)-
(1RS, 3RS) -3- (2-chloro-3,3,3-
Trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S)-
α-Cyano-m-phenoxybenzyl- (1R, 3R)
-3- (2,2-Dibromovinyl) -2,2-dimethylcyclopropanecarboxylate], cycloprothrin [(RS) -α-cyano-3-phenoxybenzyl-
(RS) -2,2-dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate], fluvalinate (α-cyano-3-phenoxybenzyl-N- (2
-Chloro-α, α, α-trifluoro-p-tolyl)-
D-Valinate, bifenthrin [(2-methylbiphenyl-3-ylmethyl)-(Z)-(1RS) -cis-
3- (2-chloro-3,3,3-trifluoroprop-
1-enyl) -2,2-dimethylcyclopropanecarboxylate], acrinathrin [[1R- {1α
(S ^* ), 3α (Z)}]-2,2-dimethyl-3-
{Oxo-3- (2,2,2-trifluoro-1- (trifluoromethyl) ethoxy-1-propenyl} cyclopropanecarboxylic acid cyano- (3-phenoxyphenyl) methyl ester], MTI-732 [2- Methyl-2-
(4-Bromodifluoromethoxyphenyl) propyl-
(3-phenoxybenzyl) ether], tralomethrin [(1R, 3S) -3-{(1′RS)-(1 ′,
2 ', 2', 2'-Tetrabromoethyl)}-2,2-
Dimethylcyclopropanecarboxylic acid- (S) -α-cyano-3-phenoxybenzyl ester], silafluofene [4-ethoxyphenyl {3- (4-fluoro-3
-Phenoxyphenyl) propyl} dimethylsilane] and the like, bubrofedin [2-tert-butylimino-3-isopropyl-5-phenyl-1,
3,5-triasianan-4-one] and other thiadiazine derivatives, imidacloprid [1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidine-2-indeneamino] and other nitroimidazolizone derivatives, cartap [S , S '-(2-Dimethylaminotrimethylene) bis (thiocarbamate), thiocyclam [N, N-dimethyl-1,2,3-trithian-5-ylamine], bensultap [S, S'-2-dimethylamino] Trimethylene di (benzenethiosulfonate)] and other nereistoxin derivatives, NI-25 [N-cyano-N′-methyl-N ′-(6-chloro-3-pyridylmethyl) acetamidine] and other cyano Amidine derivative, endosulfan [6,7,8,9,10,10-hexachloro-
1,5,5a, 6,9,9a-hexahydro-6,9-
Methano-2,4,3-benzodioxathiepine oxide], BHC [1,2,3,4,5,6-hexachlorocyclohexane], quelsen [1,1-bis- (4-chlorophenyl) -2, 2,2-Trichloroethanol]
Chlorinated hydrocarbon compounds such as chlorfluazuron [1-
(3,5-Dichloro-4- (3-chloro-5-trifluoromethylpyridin-2-yloxy) phenyl) -3
-(2,6-difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea], flufenoxuron [{1 -(4- (2
-Chloro-4-trifluoromethylphenoxy) -2-
Fluorophenyl} -3- (2,6-difluorobenzoyl) urea] and other benzoylphenylurea-based compounds, amitraz [N, N ′-{methylimino) dimethylidine} di-2,4-xylidine], chlordimeform [N′- (4-chloro-2-methylphenyl) -N,
Formamidine derivatives such as N′-dimethylmethinimidamide], thiourea derivatives such as diafenthiuron [N- (2,6-diisopropyl-4-phenoxyphenyl) -N′-tert-butylcarbodiimide], fipronil [ 5-amino-1- (2,6-dichloro-α, α, α-
Trifluoro-p-tolyl) -4-trifluoromethylsulfinylpyrazole-3-carbonitrite], tebufenozide [N-tert-butyl-N ′-(4-ethylbenzoyl) -3,5-dimethylbenzohydrazide],
MK-242 [4-bromo-2- (4-chlorophenyl) -1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrile], bromopropylate [isopropyl-4-4'-dibromobenzilate],
Tetradiphone [4-chlorophenyl-2,4,5-trichlorophenyl sulfone], quinomethionate [S,
S-6-methylquinoxaline-2,3-diyldithiocarbonate], propalgate [2- (4-tert-butylphenoxy) cyclohexylprop-2-ylsulfite], fenbutaketin oxide [bis {tris (2 -Methyl-2-phenylpropyl)} tin oxide], hexithiazox (4RS, 5RS) -5- (4
-Chlorophenyl) -N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide], clofentezine [3,6-bis (2-chlorophenyl) -1,2,4,5] -Tetrazine], pyridathiobene [2-terta-butyl-5- (4-butylbenzylthio) -4-chloropyridazin-3 (2H) one],
Fenpyroximate [tert-butyl-4-{(1,3
-Dimethyl-5-phenoxypyrazol-4-yl) methyleneaminooxymethyl} benzoate], tebufenpyrad [N- (4-tert-butylbenzyl) -4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide] , Polynactin complex [tetranactin, dinactin, trinactin], milbemectin,
Avermectin, ivermectin, azadirachtin (A
ZAD), pyrimidiphene [5-chloro-N- [2-
{4- (2-ethoxyethyl) -2,3-dimethylphenoxy} ethyl] -6-ethylpyrimidin-4-amine] and the like.

When the compound of the present invention is used as an active ingredient of an insecticidal or acaricidal agent, its application amount is about 10 are.
Usually, it is 0.1 g to 100 g, and when an emulsion, a wettable powder, a flowable agent, etc. are diluted with water and used, the application concentration is usually diluted to 0.1 ppm to 500 ppm, and an oil solution,
Apply aerosols, fumes, poison baits, etc. as they are. The application rate and application concentration depend on the type of formulation, application time, application site, application method, type of pest, and degree of damage, and should be increased or decreased regardless of the above range. You can

[0011]

EXAMPLES The present invention will be described in more detail with reference to production examples, formulation examples and test examples, but the present invention is not limited thereto. First, production examples of the compound of the present invention will be shown. Production Example 1 S-methyl-1- (dimethylcarbamoyl) -N-
5 g of [(methylcarbamoyl) oxy] thioformimidate was dissolved in 80 ml of dichloromethane and cooled to -10 ° C. While stirring, 1.84 ml of sulfur dichloride and 3.4 ml of triethylamine were successively added dropwise, and then stirring was continued at the same concentration for 1 hour. 4-chloro-4 '-(trifluoromethanesulfonyloxy) benzophenone-N-ethoxycarbonylhydrazone 10.1 g of dichloromethane 20
The ml solution and triethylamine (3.4 ml) were successively added dropwise at the same temperature, and the mixture was further reacted at the same temperature for 15 minutes. The reaction solution was poured into a large excess of saturated aqueous sodium hydrogen carbonate solution to stop the reaction. The obtained mixture was extracted with 200 ml of ethyl acetate, the organic layer was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oily substance was subjected to silica gel column chromatography, and 6.81 g of N '-[N-methyl-N- (S-
Methyl-1-dimethylcarbamoylthioformimide-N-oxycarbonyl) aminosulfenyl] -N ′
-Ethoxycarbonylhydrazono-4-chloro-4'-
(Trifluoromethanesulfonyloxy) benzophenone (Compound 21) was obtained as a mixture of four geometric isomers (resinous solid). ¹ H-NMR (TMS, CDCl ₃ ) δ (ppm): 7.17 to 7.9 (8H), 4.26 (2H, br.q), 3.34
(3H), 3.07 (6H), 2.33 (3H), 1.29 (3H)

Production Example 2 5 g of S-methyl-N-((methylcarbamoyl) oxy) thioacetamidate was dissolved in 80 ml of dichloromethane and cooled to -10 ° C. Sulfur dichloride 2.
After successively adding 35 ml and 4.32 ml of triethylamine, stirring was continued at the same temperature for 1 hour. To this, 4-chloro-4'-
A solution of 13 g of (trifluoromethanesulfonyloxy) benzophenone-N-ethoxycarbonylhydrazone in 20 ml of dichloromethane and 4.32 ml of triethylamine were successively added dropwise at the same temperature, and the mixture was further reacted at the same temperature for 20 minutes. The reaction solution was poured into a large excess of saturated aqueous sodium hydrogen carbonate solution to stop the reaction. The obtained mixture was extracted with 200 ml of ethyl acetate, the organic layer was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography, and 5.03 g of N '-[(N-methyl-N- (S-methyl-thioacetimide-N-oxycarbonyl) aminosulfenyl] -N'-ethoxycarbonyl was obtained. Hydrazono-4-chloro-4 ′-(trifluoromethanesulphonyloxy) benzophenone (Compound 1
2) was obtained as a mixture of 4 geometric isomers (resinous solid). ¹ H-NMR (TMS, CDCl ₃ ) δ (ppm): 7.17 to 7.9 (8H), 4.26 (2H, br.q), 3.34
(3H), 3.07 (6H), 2.33 (3H), 1.29 (3H)

Examples of the compounds of the present invention are shown in Tables 1 to 6.
(Indicated by the definition of the substituent of the compound represented by the general formula: 3)

[Table 1]

[0014]

[Table 2]

[Table 3]

[0015]

[Table 4]

[Table 5]

[0016]

[Table 6]

Formulation examples are shown below. In addition, a part represents a weight part. Formulation Example 1 Emulsion 10 parts of each of the compounds 1 to 124 of the present invention were dissolved in 35 parts of xylene and 35 parts of dimethylformamide, 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate were added, and well mixed by stirring. To obtain each 10% emulsion. Formulation Example 2 Emulsion 20 parts of each of the compounds of the present invention 1 to 124 were added to a mixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of diatomaceous earth, and a juice mixer was used. Stir-mix to obtain each 20% wettable powder. Formulation Example 3 Granules 5 parts of the compound 1 or 2 of the present invention, 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate,
Bentonite (30 parts) and clay (55 parts) are added and thoroughly mixed with stirring. Then, an appropriate amount of water is added to these mixtures, further stirred, granulated by a granulator, and dried by ventilation to obtain 5%.
Get granules. Formulation Example 4 Dust agent 1 part of each of the compounds 1 to 124 of the present invention was dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder and PAP were added thereto.
0.3 part and 93.7 parts of clay are added, and the mixture is stirred and mixed with a juice mixer, and acetone is removed by evaporation to obtain each 1% powder. Formulation Example 5 Flowable Agent 20 parts of 1 or 2 of the compound of the present invention and 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and finely ground by a sand glider (particle size 3 μ or less). After that, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate was added thereto, and further 1 part of propylene glycol was added.
Add 0 parts and stir-mix to obtain a 20% suspension in water. Formulation Example 6 Oil formulation Each of 1-124 of the compound of the present invention and 0.1 part of xylene 5
Parts and trichloroethane (5 parts) and mixed with 89.9 parts of deodorized kerosene to obtain 0.1 parts of each oil solution. Formulation Example 7 Oily aerosol 0.1 part of each of the compounds of the present invention 1-1, 0.2 part of tetramethrin, 0.1 part of d-phenothrin, 10 parts of trichloroethane and 59.6 parts of deodorized kerosene were mixed and dissolved, and filled in an aerosol container. Then, after the valve portion is attached, 30 parts of propellant (liquefied petroleum gas) is charged under pressure through the valve portion to obtain each oil-based aerosol. Formulation Example 8 Aqueous Aerosol 0.2 part of each of the compounds of the present invention 1-2, d-allethrin 0.2 part, d-phenothrin 0.2 part, xylene 5 parts, deodorant kerosene 3.4 parts and emulsifier {Atmos 300. (Registered trademark name of Atlas Chemical Co., Ltd.)}
50 parts of pure water is filled in an aerosol container, a valve portion is attached, and 40 parts of a propellant (liquefied petroleum gas) is filled under pressure through the valve portion to obtain each aqueous aerosol.

Next, it will be shown by test examples that the compound of the present invention is useful as an active ingredient of insecticides and acaricides. The compounds of the present invention are shown by the compound numbers shown in Tables 1 to 6. Test Example 1 (Insecticidal test against Spodoptera litura) According to Formulation Example 1, the test compound was made into an emulsion, and 2 ml of the diluted solution (500 ppm) with water was prepared in advance in a polyethylene cup with a diameter of 11 cm. It was soaked in 13 g of feed. Ten fourth-instar larvae of Hanmoyoto were released into the larvae, and after 6 days, their life and death were examined to determine the mortality rate. As a result, compounds (12) and (21) showed a mortality of 100%. The untreated plot had a mortality rate of 0%. Test Example 2 (Ovicidal and Larvicidal Tests against diamondback moth) A test compound was made into an emulsion according to Formulation Example 1, and a diluted solution (50 ppm) thereof with water to lay 100 to 150 diamondback moth eggs after seeding Soak 2 radish sprouts for 5 to 6 days and 2 radish sprouts for laying eggs for a total of 30 seconds, let them air dry, and put them in a 5.5 cm diameter polyethylene cup.
After the day, the presence or absence of hatching and the mortality of larvae were investigated, and the ovicidal rate and the larvicidal rate were calculated. The criteria for judgment are as follows. a: 100% ovicidal or larvicidal rate b: 90% or more and less than 99% ovicidal or larvicidal rate c: 90% or less ovicidal or larvicidal rate As a result, compounds (12) and (21) a was shown. In addition, the untreated section showed c. Test Example 3 (Insecticidal test for larvae of brown planthopper) Rice stalks (about 5 cm in length) were immersed for 1 minute in a diluted solution (500 ppm) of the emulsion of the test compound obtained according to Formulation Example 1 in water. After air drying, a 5.5 cm diameter filter paper containing 1 ml of water was laid. Rice stalks were placed in a polyethylene cup having a diameter of 5.5 cm, and about 30 larvae of the brown planthopper were released therein, and their life and death were examined 6 days later. The criteria for effect evaluation are: a: No live insects are observed. b: Five or less surviving insects are recognized. c: Six or more live insects are recognized. As a result, the compounds (12) and (21) showed a. In addition, the untreated section showed c. Test Example 4 (Insecticidal test against Southern corn rootworm larvae) A polyethylene cup having a diameter of 5.5 cm was covered with a filter paper of the same size, and an emulsion of the test compound obtained according to Formulation Example 1 was diluted with water. 1 ml (500 ppm) was dropped on the filter paper. Approximately 30 Southern corn rootworm eggs were placed on this filter paper, and 1 corn sprouting was put in as bait. After 8 days, the survival of dead larvae was investigated. The effect evaluation criteria were as follows: a: 100% mortality, b: 99-90% mortality, c: 90% mortality. As a result, the compounds (12) and (21) are a
showed that.

Test Example 5 (Insecticidal test against housefly) A polyethylene cup having a diameter of 5.5 cm was covered with a filter paper of the same size, and an emulsion of the test compound obtained according to Formulation Example 1 was diluted with water ( 0.7 ml of 500 ppm) was dropped on the filter paper, and about 30 mg of sucrose was uniformly added as a bait. Ten adult houseflies were released in the flask, the lid was put on, and one day later, the life and death thereof were examined to determine the mortality rate. As a result, the compounds (12) and (21) showed a mortality of 80% or more. The untreated sample showed a mortality of 0%. Test Example 6 (Insecticidal test against German cockroaches) A polyethylene cup having a diameter of 5.5 cm was covered with a filter paper of the same size, and an emulsion of the test compound obtained according to Formulation Example 1 was diluted with water (500 ppm). 0.7 ml was dropped on the filter paper, and about 30 mg of sucrose was uniformly added as a bait. Ten adult German cockroaches were released therein, the lid was put on, and the life and death thereof were examined 6 days later, and the mortality rate was calculated. As a result, compounds (12) and (21) showed a mortality of 100%. The untreated sample showed a mortality of 0%. Test Example 7 (Insecticidal test against Culex pipiens) A compound to be tested was made into an emulsion according to Formulation Example 1, diluted with water, and 0.7 ml of the solution was added to 100 ml of ion-exchanged water (concentration of active ingredient: 3.5 ppm). ). 20 dead larvae of Culex pipiens were released in it, and the mortality rate after 1 day was investigated. The criteria for effect evaluation are as follows: a: mortality rate of 90% or more b: mortality rate of 10% or more and less than 90% c: mortality rate of less than 10%. As a result, the compounds (12) and (21) are a
showed that. In addition, the untreated section shows c. Test Example 8 (Insecticidal test against cotton aphid) According to Formulation Example 1, an emulsion of the test compound was diluted to a predetermined concentration with water, and then added to a polyethylene cup planted cucumber plant.
Irrigation was performed at a rate of 10 cc / 1 pot. Three days after the treatment with the drug solution, five adult aphids were released on the true leaves. Six days after the release, the number of surviving insects was counted. The effect evaluation criteria were as follows: a: live worms 0 b: live worms 1-10 c: live worms 10 or more. As a result, the compounds (12) and (21) are a
showed that. In addition, the untreated section shows c. Test Example 9 (Insecticidal test against Mite spider mite) Ten days ago, ten adult females of Mite spider mite were infested with the potted flesh bean plant (primary leaf stage) 7 days after sowing.
It was placed in a thermostatic chamber at 5 ° C. Six days later, the test compound was made into an emulsion according to Formulation Example 1, and a chemical solution diluted with water to 500 ppm of the active ingredient was sprayed on the turntable in an amount of 15 ml per pot, and 2 ml of the same solution was simultaneously irrigated with soil. After 8 days, the degree of damage of each plant due to spider mites was investigated. The criteria for effectiveness are: -No damage is observed. +: Some damage is recognized. ++: The same damage as in the untreated area is recognized. And As a result, the compound (21) showed-.

[0020]

The compounds of the present invention exhibit excellent insecticidal and acaricidal effects.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Kishida 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Shigeru Saito 4-2-1 Takashi Takarazuka-shi, Hyogo Prefecture Sumitomo Chemical Co., Ltd.

Claims (2)

[Claims] 1. A general formula: ## STR1 ## [In the formula, X represents a halogen atom, R ¹ represents a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, a cyano group or an alkoxy group having 1 to 3 carbon atoms. Represents a group or an alkoxy group having 1 to 4 carbon atoms which may be substituted with a halogen atom. R ² represents a trifluoromethyl group or a methyl group, R ³ and R ⁴ are the same or different and represent a hydrogen atom, or an alkylthio group having 1 to 4 carbon atoms, an alkylsulfinyl group having 1 to 4 carbon atoms, Carbon number 1
Represents an alkylsulfonyl group having 1 to 4 carbon atoms which may be substituted with an alkylsulfonyl group or cyano group,
Alternatively, a carbon number of 1 to 1 which may be substituted with a cyano group.
4 represents an alkylthio group of 4 or represents a phenyl group which may be substituted with a halogen atom, or represents a compound represented by the general formula: (In the formula, R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). n represents 0 or 1. ] The hydrazone compound shown by these. 2. An insecticidal and acaricidal agent containing the hydrazone compound according to claim 1 as an active ingredient.