JPH07149708A - Hydrazone compound and insecticide containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To provide a novel hydrazone compound exhibiting an excellent insecti cidal potency, relatively low in acute toxicity against mammalians, and useful as an insecticide. CONSTITUTION:A hydrazone compound is expressed by formula I (R<1>, R<2> are H, 1-2C alkyl, 1-2C alkoxy, methoxymethyl, cyanomethyl; but R<1> and R<2> are simultaneously not H; R<3> is trifluoromethyl, methyl; X is halogen), e.g. 4- chloro-4'-(trifluoromethylsulfonyloxy) benzophenone-N',N'-diacetylhydrazone. The compound of formula is obtained e.g. by reacting a compound of formula II with a compound of formula III (Z is Cl, Br, -OCOR<2>, methoxy, ethoxy, OH; but when Z is OH, R<2> is 1-2C alkoxy). The compound of formula I includes further 4-chloro-4'(trifluoromethylsulfonyloxy)benzophenoneN',N'-(ethoxycarbonyl) hydrazone in addition to the above-mentioned example.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a hydrazone compound and an insecticide containing the same as an active ingredient.

2. Description of the Related Art Conventionally, for example, US Pat. No. 4,344,893 discloses that certain hydrazone compounds can be used as active ingredients of insecticides. However, the compound has not been put into practical use due to problems such as acute toxicity to mammals.

In view of such a situation, the present inventors have conducted extensive studies to find a compound having an excellent insecticidal effect and low toxicity to mammals, and as a result, the following general formula was obtained. It was found that the hydrazone compound represented by Chemical formula 2 has an excellent insecticidal efficacy and has relatively low acute toxicity to mammals, and completed the present invention. That is, the present invention has the general formula

[Chemical 2][In the formula, R¹And R²Are the same or different and
Child, alkyl group having 1 to 2 carbon atoms (methyl group or ethyl
Group), an alkoxy group having 1 to 2 carbon atoms (methoxy group or
Ethoxy group), methoxymethyl group or cyanomethyl group
Represents However, R ¹And R²Are not hydrogen atoms at the same time.
R³Represents a trifluoromethyl group or a methyl group, and X
Is a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine
Elementary atom). ] A hydrazone compound represented by
Hereinafter, the compound of the present invention is described. ) And that as an active ingredient
Insecticide is provided.

The compound of the present invention can be produced, for example, by the following production method A.
Alternatively, it can be manufactured by the manufacturing method B. (Production Method A) General Formula 3

[Chemical 3] [In the formula, R ¹ , R ³ and X have the same meanings as described above. ] The compound represented by the following general formula:

[Chemical 4][In the formula, R²Represents the same meaning as above, and Z represents chlorine source.
Child, bromine atom, -OCOR ²A group represented by
2 alkoxy groups (methoxy or ethoxy groups),
Or represents a hydroxyl group. However, when Z represents a hydroxyl group,
R²Is not an alkoxy group having 1 to 2 carbon atoms. ]]
A method for producing a compound by reacting with a compound described above. Made
A solvent is not always necessary in the manufacturing method A, but
Is preferably carried out in an inert organic solvent.
If it is, it goes without saying that it is used properly according to the type of Z
But generally, for example, benzene, toluene, xyle
Aromatics such as benzene, chlorobenzene, and o-dichlorobenzene
Hydrocarbons, pyridines such as pyridine and picoline, black
Loform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1
-Trichloroethane, tetrachloroethylene, trichlor
Halogenated hydrocarbons such as polyethylene, n-hexane,
Aliphatic hydrocarbons such as n-heptane, cyclohexane, etc.
Alicyclic hydrocarbons, methanol, ethanol, isop
Alcohols such as lopanol, N, N dimethylformua
Aprotic polar solvents such as amide and dimethyl sulfoxide
Medium, tetrahydrofuran, diethyl ether, etc.
And ketones such as acetone and methyl isobutyl ketone
A class, water, etc., or a mixed solvent thereof is used. Manufacturing
In the method A, in the compound of the general formula 3, Z is a chlorine atom,
Bromine atom, OCOR²Or a group having 1 to 2 carbon atoms
When the alkoxy group is represented by
Do below. Examples of the base used include triethyl
Amine, pyridine, 4-N, N-dimethylaminopyridi
Organic bases such as N, N, N-diethylaniline, sodium hydroxide
Inorganic salts such as thorium, sodium hydride, potassium carbonate
Group, butyllithium, lithium diisopropylamide, etc.
And the like. In manufacturing method A,
When Z is a hydroxyl group in the compound of general formula 3,
Is usually performed in the presence of a condensing agent. As a condensing agent used
Include, for example, organic compounds such as tosylic acid chloride and pivaloyl chloride.
Lewis acid such as acid chloride, titanium tetrachloride and dicyclohexyl
Removal of xylcarbodiimide, phosphorus pentoxide, polyphosphoric acid, etc.
Examples include liquid medicines. Reaction test used in production method A
The amount of the agent is 1 mol of the compound represented by the general formula:
The base and the condensing agent are usually in a proportion of 0 to 100 mol.
In the case of the compound represented by the general formula 4,
The reaction temperature of the reaction is usually -20 to 200.
The reaction temperature is usually 5 minutes to 100 hours. End of reaction
After completion, perform normal post-treatment such as organic solvent extraction and concentration.
The desired compound of the present invention can be isolated by
It Chromatography or recrystallization, if necessary
It can be further purified by the method.

The compound represented by the general formula 3 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) General Formula 5

[Chemical 5] [In the formula, R ³ and X have the same meanings as described above. ] And the compound represented by the general formula:

[Chemical 6] [In the formula, Z and R ¹ have the same meanings as described above. ] The method of making it react with the compound shown by these. In the production method, 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 goes without saying that they are used properly depending on the type of Z,
Generally, for example, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and o-dichlorobenzene, pyridines such as pyridine and picoline, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1, Halogenated hydrocarbons such as 1,1-trichloroethane, tetrachloroethylene and trichloroethylene, aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane, alcohols such as methanol, ethanol and isopropanol Aprotic polar solvent such as N, N-dimethylformamide, dimethylsulfoxide,
Ethers such as tetrahydrofuran and diethyl ether, ketones such as acetone and methyl isobutyl ketone,
Water or 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 ² or an alkoxy group having 1 to 2 carbon atoms in the compound of the general formula 6, the reaction may be 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-diethylaniline, inorganic bases such as sodium hydroxide, sodium hydride and potassium carbonate, butyl lithium. , Organic metal bases such as lithium diisopropylamide, and the like. In addition, the general formula
When Z represents a hydroxyl group in the compound (1), 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 acid 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 0 to 100 mol of the base and the condensing agent with respect to 1 mol of the compound represented by the formula 5, and the compound represented by the general formula 6 is usually 1 to 1. The reaction temperature of the reaction is usually -20 to 200 ° C, and the reaction time is usually 5 minutes to 100 hours. After completion of the reaction, by performing usual post-treatments such as organic solvent extraction and concentration,
The compound represented by the general formula 3 can be isolated. The compound represented by the general formula 3 produced by such a method can also be used in the reaction of the production method A without isolation.

When R ² is the same as R ^{1 in the} compound of the present invention, the compound of the present invention can also be produced by the production method B shown below. (Production Method B) A method of reacting the compound represented by the formula (5) with the compound represented by the general formula (6). In the production method B, 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 goes without saying that it is properly selected depending on the type of Z, but generally, for example, benzene. , Aromatic hydrocarbons such as toluene, xylene, chlorobenzene and o-dichlorobenzene, pyridines such as pyridine and picoline, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1
-Halogenated hydrocarbons such as trichloroethane, tetrachloroethylene, trichloroethylene and the like. n-hexane,
Aliphatic hydrocarbons such as n-heptane, alicyclic hydrocarbons such as cyclohexane, alcohols such as methanol, ethanol and isopropanol, aprotic polar solvents such as N, N-dimethylformamide and dimethylsulfoxide, tetrahydrofuran, Ethers such as diethyl ether, ketones such as acetone and methyl isobutyl ketone, water and the like or a mixed solvent thereof are used. In the production method B, in the compound of the general formula 6, Z is a chlorine atom, a bromine atom, a group represented by OCOR ² or a carbon number 1
When representing an alkoxy group of ~ 2, the reaction may be carried out in the presence of a base. Examples of the base used include organic bases such as triethylamine, pyridine, 4-N, N-dimethylaminopyridine and N, N-diethylaniline,
Examples thereof include inorganic bases such as sodium hydroxide, sodium hydride and potassium carbonate, and organic metal bases such as butyllithium and lithium diisopropylamide. When Z is a hydroxyl group in the compound of general formula 6, 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 acid chloride and pivaloyl chloride, Lewis acids such as titanium tetrachloride, and dehydrating agents such as dicyclohexylcarbodiimide, phosphorus pentoxide, and polyphosphoric acid. In the production method B, the amount of the reaction reagent used is usually 0 to 100 mol of the base and the condensing agent, and 1 mol of the compound of the general formula 6 is usually used, relative to 1 mol of the compound of the general formula 5. The reaction temperature of the reaction is usually -20 to 20.
The reaction time at 0 ° C 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 a usual post-treatment.

The compound represented by the general formula 5 used as the starting compound of the production method a and the starting compound of the production method B can be produced, for example, by the method described in US Pat. No. 4,344,893. The compound of the present invention includes
There are two geometric isomers depending on the configuration of the C = N double bond of the hydrazone moiety.
The geometric isomers of the species (E and Z) and mixtures thereof are included.

Examples of the pests for which the compound of the present invention has a controlling effect include the following. Hemiptera pests: Brown Planthopper ( Laodelphax striatellus) , Brown Planthopper ( Nilaparvata lugens ), White- tailed Planthopper ( So
gatella furcifera) planthoppers, such as green rice leafhopper (Nephotettix cincticeps), leafhoppers, such as Taiwan green rice leafhopper (Nephotettix virescens), aphids, stink bugs, whiteflies, scale insects, tingidae class, Lepidoptera rice stem borer, such as psyllid acids (Chilo suppressalis ), Kobunomeiga
( Cnaphalocrocis medinalis ), European corn borer ( Ostrinia nubilalis ), Shibattoga ( Pa
rapediasia teterrella ), Watanomaiga ( Notarcha )
derogata ), Pyrophora interpuncta ( Plodia interpunct)
Ella and other common moths , Spodoptera litura ( Spodoptera
litura), armyworm (Pseudalitia separata), cabbage armyworm (Mamestra brassicae), black cutworm (Agroti
s ipsilon ), Turkish Prussia, Heliotis,
Long-tailed moths such as Helicopterpa and Pieris
rapae crucivora ) and other white butterflies, Adoxophyes spp., Grapholita molesta
), Codling moss ( Cydia pomonella ), and other leaf tortoises, Peach moth ( Carposina niponensis )
Shinkuiga such, Hamoguriga such as Rionetia genus Rimantoria genus, tussock such as user Proc-Eustis genus, such as diamondback moth (Plutella xylostella) Suga such as, pink bollworm (Pectinophora gossypiella) Kibaga such as, the United States white Arctiidae (Hyphantria cunea) Hitriggers such as, Moth ( Tinea translucens ), Koga
(Tineola bisselliella) Hirozukoga such like Diptera Culex (Culex pipiens pallens), such as, Culex such as Culex (Cules tritaeniorhynchus), Aedes aegypti, Aedes spp such as Aedes albopictus, Anopheles spp such as Anopheles sinensis,
House flies such as chironomids , house flies ( Musca domestica ), house flies ( Muscina stabulans ), blow flies, flesh flies, house flies, sand flies ( De)
lia platura ), onion fly ( Delia antigua )
Western corn rootworm ( Diabrotica virgifer ) such as fruit flies, fruit flies, fruit flies, butterfly flies, gnats , flies, flies, leaf flies, etc.
a ) the Southern corn rootworm ( Diabrotica undeci
mpunctata ) and other corn rootworms, Rana bursa ( Anomala cuprea ), and Scutellaria ( Anomala )
chafers such as rufocuprea ), Maysweville
( Sitophilus zeamais ), rice weevil ( Lissorh
optrus oryzophilus ), alfalfa weevil ( Hypera pastica ), adzuki bean weevil ( Calosobruchy )
s chienensis) weevils such as, chai loco Meno mealworm (Tenebrio molitor), mealworm such as red flour beetle (Tribolium castaneum), cucurbit leaf beetle (Aulacophora femoralis), Kisujinomihamushi (Phyllotreta striolata), beetles such as Colorado potato beetle (Leptinotarsa decemlineata) ,
Anemone beetle, Epilachna
Vigintioctopunctata) Epilachna such as, Hirata beetles such, Naga Shinkuimushi acids, Cerambycidae such, Aoba ants backlash Staphylinidae (Paederus fuscipes), etc. Orthoptera network Orthoptera pests German cockroach (Blattella germanica), black cockroach (Periplaneta fuliginosa), American cockroach (P
eriplaneta americana ), Black-tailed Cockroach ( Perip
laneta brunnca ), American cockroach ( Blatta ori
entalis) Thysanoptera South thrips such as (Thrips palmi), green onion thrips (Thrips tabaci), Hana thrips (Thrips
hawaiiensis), 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) It is effective against the isoptera pests such as Reticulitermes speratus and Coptotermes formosanus . It is also effective against pests that have developed resistance to existing insecticides.

When the compound of the present invention is used as an active ingredient of an insecticide, it may be used as it is without adding any other ingredients, but it is usually used as a solid carrier, liquid carrier, gaseous carrier, bait or the like. Mix and add surfactants and other formulation aids if necessary to formulate oils, emulsions, wettable powders, flowables, granules, powders, aerosols, fumes (fogging, etc.), poison baits, etc. To use. These formulations include
The compound of the present invention as an active ingredient is usually 0.01% by weight.
~ 95% content. Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (serisite, quartz, Sulfur, activated carbon, calcium carbonate,
Hydrated silica, etc., chemical fertilizers (ammonium sulfate, phosphorus ammonium, ammonium nitrate, urea,
Examples of liquid carriers include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, benzene, etc.). Toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic 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-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, soybean oil, vegetable oils such as cottonseed oil, and the like, and a gaseous carrier, that is, a propellant, Examples thereof include CFC gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas and the like. Examples of the surfactant include alkyl sulfate 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 give. Examples of formulation adjuvants 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). , Polyvinylpyrrolidone, polyacrylic acids, etc., and examples of the stabilizer include PAP (isopropyl acid phosphate) and BH.
T (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil , Surfactants, fatty acids or esters thereof, and the like. As a base material for poison baits, for example, cereal flour, vegetable essential oil, sugar, bait components such as crystalline cellulose, dibutylhydroxytoluene, antioxidants such as nordihydroguaiaretic acid, preservatives such as dehydroacetic acid,
Examples include an accidental food ingestion agent such as pepper powder, a cheese flavor, and an attractive flavor such as onion flavor.

The thus obtained preparation is used as it is or diluted with water or the like. Also other pesticides,
It can be used simultaneously with or without mixing with nematicides, acaricides, fungicides, herbicides, plant production regulators, synergists, fertilizers, soil conditioners, animal feeds and the like. Examples of the insecticide, nematicide and acaricide used include fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate] and fenthion [O, O-dimethyl O- (3 -Methyl-4-
(Methylthio) phenyl) phosphorothioate], diazinon [O, O-diethyl-O-2-isopropyl-
6-methylpyrimidin-4-yl phosphorothioate], chlorpyrifos [O, O-diethyl-O-3,
5,6-Trichloro-2-pyridylphosphorothioate], acephate [O, S-dimethylacetylphosphoramidothioate], methidathion [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4- Thiadiazol-3-ylmethyl O, O-dimethyl phosphorodithioate], disulfoton [O, O-diethyl S
2-Ethylthioethyl phosphorothioate], DDV
P [2,2-dichlorovinyl dimethyl phosphate],
Sulprophos [O-ethyl O-4- (methylthio) phenyl S-propyl phosphorodithioate], cyanophos [O-4-cyanophenyl O, O-dimethylphosphorothioate], 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 2,2,2,2] Two
-Trichloro-1-hydroxyethylphosphonate],
Azinphos-methyl [S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethyl,
O, O-dimethyl phosphorodithioate], monocrotophos [dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate], ethione [0,0,
0 ', 0'-tetraethyl S, S'-methylenebis (phosphorodithioate)] and other organic phosphorus compounds, B
PMC [2-sec-butylphenylmethylcarbamate], benfuracarb [ethyl N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-
β-alaninate], propoxur [2-isopropoxyphenyl N-methylcarbamate], carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzo [b] furanyl N-dibutylaminothio-N-methyl Carbamate], carbaryl [1-naphthyl-N-methylcarbamate], Methomyl [S-methyl-N-
[(Methylcarbamoyl) oxy] thioacetimidate], Ethiophencarb [2- (ethylthiomethyl)]
Phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-
Methylcarbamoyl oxime], oxamyl [N, N-
Dimethyl-2-methylcarbamoyloxyimino-2-
(Methylthio) acetamide], phenothiocarb [S-
4-phenoxybutyl) -N, N-dimethylthiocarbamate] and other carbamate compounds, etofenprox [2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether], fenvalerate [(RS ) -Α-Cyano-3-phenoxybenzyl (RS) -2- (4-chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-3-phenoxybenzyl (S) -2 -(4-chlorophenyl) -3-methylbutyrate], phenpropatoline [(RS) -α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [( RS) -α-cyano-3-phenoxybenzyl (1RS, 3RS)-(1R
S, 3RS) -3- (2,2-dichlorovinyl) -2,
2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS, 3RS)
-(1RS, 3RS) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], cyhalothrin [(RS) -α-cyano-3-phenoxybenzyl (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 ([1
R- {1α (S ^* ), 3α (Z)}]-2,2-dimethyl-3- [3-oxo-3- (2,2,2-trifluoro-1- (trifluoromethyl) ethoxy- 1-Propenyl] cyclopropanecarboxylic acid cyano (3-phenoxyphenyl) methyl ester, TI-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 other pyrethroid compounds, buprofezin (2-tert-butylimino-3-)
Thiadiazine derivatives such as isopropyl-5-phenyl-1,3,5-triadiazan-4-one), imidacloprid [1- (6-chloro-3-pyridylmethyl)-
N-nitroimidazolidine-2-indenamine] and other nitroimidazolidine derivatives, cartap (S, S'-
(2-Dimethylaminotrimethylene) bis (thiocarbamate)], thiocyclam [N, N-dimethyl-1,
2,3-trithian-5-ylamine], bensultap [S, S′-2-dimethylaminotrimethylene di (benzenethiosulfonate)], and other nereistoxin derivatives, MI-253 [N-cyano-N ′]. -Methyl-N '
N-cyanoamidine derivatives such as-(6-chloro-3-pyridylmethyl) acetamidine] and endosulfan [6,7,8,9,10,10-hexachloro-1,
5,5a, 6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine oxide], γ-BHC (1,2,3,4,5,6-hexachlorocyclohexane ], Chlorene hydrocarbon compounds such as Kelsen [1,1-bis (chlorophenyl) -2,2,2-trichloroethanol], 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 the like, benzoylphenylurea compounds,
Amitraz [N, N '[(methylimino) dimethylidine] di-2,4-xylidine], chlordimeform [N'-(4-chloro-2-methylphenyl) -N, N
-Dimethylmethinimidamide] and other formamidine derivatives, diafenthiuron [N- (2,6-diisopropyl-4-phenoxyphenyl) -N'-tert-butylcarbodiimide] and other thiourea derivatives, 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],
Chlorphenapyr [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-yl sulfite], fenbutatin 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, pyridaben [2-tert-butyl-5- (4-tert-butylbenzylthio) -4-chloropyridazin-3 (2H) -one], fenpyroximate [tert-butyl (E) -4
-[(1,3-Dimethyl-5-phenoxypyrazole-
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 [AZAD], pyrimidifen [5-chloro-
N- [2- {4- (2-ethoxyethyl) -2,3-dimethylphenoxy} ethyl] -6-ethylpyrimidine-
4-amine etc. are mentioned.

When the compound of the present invention is used as an agricultural insecticide, its application amount is usually from 0.1 g to 10 are.
It is 100 g, and when an emulsion, wettable powder, flowable agent, etc. are diluted with water, the application concentration is usually 0.1 ppm to
It is 500ppm, and granules, powders, etc. are applied as they are without any dilution. When used as an insecticide for epidemic prevention, emulsions, wettable powders, flowable agents, etc. are usually diluted with water to a concentration of 0.1 ppm to 500 ppm, and then applied.
Apply aerosols, fumes, poison baits, etc. as they are. The application amount and application concentration depend on the type of formulation, application time, application site, application method, pest type, degree of damage, etc., and may be increased or decreased without regard to the above range. can do.

Hereinafter, 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 4-Chloro-4'-trifluoromethylsulfonyloxybenzophenone-N'-acetylhydrazone A solution of 0.5 g of N, N-dimethylformamide (4 ml) was stirred at room temperature while adding sodium hydride 60% thereto. 0.1 g of an oil mixture of sodium hydride containing (W / W) was added at once. After stirring at room temperature for 15 minutes to stop generation of hydrogen gas, 1 ml of acetyl chloride was added at once. After further stirring at room temperature for 10 minutes, the reaction mixture was poured into ice water.
The aqueous layer was extracted with ethyl acetate, the organic layers were combined, washed successively with water, diluted hydrochloric acid and saturated aqueous sodium hydrogen carbonate, and then dried over anhydrous magnesium sulfate. The residue obtained by concentration is subjected to silica gel column chromatography to obtain 0.4 g of desired 4-chloro-4′-trifluoromethylsulfonyloxybenzophenone-N ′, N′-diacetylhydrazone (Compound 1). It was n _D ^24.8 1.5432 Preparation Example 2 4-chloro-4′-trifluoromethylsulfonyloxybenzophenonehydrazone 0.5 g of pyridine (4 ml)
While stirring the solution at room temperature, 1.5 ml of methoxyacetyl chloride was added thereto all at once. After stirring at room temperature for 3 hours, the reaction mixture was poured into water. The aqueous layer was extracted with ethyl acetate, the organic layers were combined, washed successively with water, diluted hydrochloric acid and saturated aqueous sodium hydrogen carbonate, and then dried over anhydrous magnesium sulfate. The residue obtained by concentration is subjected to silica gel column chromatography to obtain the desired 4-chloro-4′-trifluoromethylsulfonyloxybenzophenone-N ′, N ′.
-Di (methoxyacetyl) hydrazone (Compound 15) 0.
2 g was obtained as a resinous material. H ¹ -NMR (TMS, CDCl ₃ ) δ (ppm): 7.0 to 8.0 (8H), 4.35 (2H, s), 4.
33 (2H, s), 3.31 (3H, s), 3.28 (3H, s)

Examples of the compounds of the present invention are shown in Tables 1-8.
(Indicated by the respective substituents of the general formula 2)

[Table 1]

[0012]

[Table 2]

[0013]

[Table 3]

[0014]

[Table 4]

[0015]

[Table 5]

[0016]

[Table 6]

[0017]

[Table 7]

[0018]

[Table 8]

Next, formulation examples are shown. In addition, a part represents a weight part. Formulation Example 1 Emulsion 10 parts of each of the compounds of the present invention 1-121 were dissolved in 35 parts of xylene and 35 parts of dimethylformamide, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate were added, and the mixture was stirred well. Obtain each 10% emulsion. Formulation Example 2 Wettable Powder 20 parts of each of the compounds of the present invention 1-121 are added to a mixture of 4 parts of sodium lauryl sulfate, 4 parts of calcium ligninsulfonate, 20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of diatomaceous earth, and juice. Stir-mix with a mixer to obtain each 20% wettable powder. Formulation Example 3 Granules (in the case of solid drug substance) 5 parts of each of Compounds 4 and 14 of the present invention, 5 parts of synthetic hydrous silicon oxide fine powder, and 5 parts of sodium dodecylbenzenesulfonate
Part, bentonite 30 parts and clay 55 parts are added and mixed thoroughly with stirring. Then, an appropriate amount of water is added to these mixtures, the mixture is further stirred, granulated by a granulator, and air-dried to obtain each 5% granule. Formulation Example 3 ′ Granule (in the case of liquid drug substance) Compounds of the present invention 1 to 3, 5 to 13, 28, 43, 57, 8
8 parts to each 5 parts sodium dodecylbenzene sulfonate 5 parts, bentonite 30 parts and clay 60 parts,
Mix well with stirring. Then, an appropriate amount of water is added to these mixtures, and the mixture is further stirred, granulated by a granulator, and dried by ventilation to obtain each 5% granule. Formulation Example 4 Dust agent 1 part of each of the compounds 1-121 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 dissolved in the solution.
0.3 parts 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 (in the case of solid drug substance) 20 parts of each of the compounds 4 and 14 of the present invention and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and a sand grinder was used. After finely pulverizing (particle size 3μ or less) with, xanthan gum
40 parts of an aqueous solution containing 05 parts and 0.1 part of aluminum magnesium silicate is added, 10 parts of propylene glycol is further added, and the mixture is stirred and mixed to obtain each 20% suspension in water. Formulation Example 5 ′ Flowable agent (in the case of liquid drug substance) Compounds of the present invention 1 to 3, 5 to 13, 28, 43, 57, 8
10 parts of each of 8 are added to 40 parts of an aqueous solution containing 6 parts of polyvinyl alcohol and stirred with a mixer to obtain a dispersant.
To this, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate was added, and further 10 parts of propylene glycol was added thereto and gently mixed with stirring to obtain each 10% emulsifier in water. Formulation Example 6 Oil formulation Each 0.1 parts of the compounds of the present invention 1-121 was dissolved in 5 parts of xylene and 5 parts of trichloroethane, and this was deodorized kerosene 8
Mix to 9.9 parts to give each 0.1% oil. Formulation Example 7 Oily aerosol 0.1 parts of each of the compounds 1-121 of the present invention, tetramethrin
0.2 part, d-phenothrin 0.1 part, trichloroethane 1
After mixing and dissolving 0 parts and 59.6 parts of deodorized kerosene and filling the aerosol container with the valve part attached, 30 parts of the propellant (liquefied petroleum gas) was pressure-filled through the valve part to obtain each oil-based aerosol. To get Formulation Example 8 Aqueous aerosol 0.2 parts of each of the compounds 1-121 of the present invention, d-allethrin
0.2 parts, 0.2 part of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorizing kerosene and 1 part of emulsifier {Atmos 300 (registered trade name of Atlas Chemical Co.)} were mixed and dissolved, and 50 parts of pure water. Fill the aerosol container with and, and attach the valve part, through the valve part the propellant (liquefied petroleum gas)
40 parts under pressure are filled 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 an insecticide. The compounds of the present invention are shown by the compound numbers shown in Tables 1 to 8, and the compounds used for comparison and control are shown by the following compound symbols. Compound A: 4-chloro-4 ′-(trifluoromethylsulfonyloxy) benzophenone-N′-acetylhydrazone (compound contained in general formula described in US Pat. No. 4,344,893) Compound B : 4-chloro-4 ′-(trifluoromethylsulfonyloxy) benzophenone-N ′-(ethoxycarbonyl) hydrazone (US Pat. No. 4,344,89
Compound No. 83 described in No. 3 patent specification column 20) Test Example 1 (Insecticidal test against Spodoptera litura) A test compound was made into an emulsion according to Formulation Example 1, and 2 ml of its diluted solution (500 ppm) in water was added to a solution of A polyethylene cup was soaked with 13 g of the artificial feed for Haemus Yodo that had been prepared in advance. 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, the following compounds showed 100% mortality. (1 2 3 4 5 6 7 8) ,
(9), (10), (11), (12), (13), (14), (15), (28), (4
3), (57), (88) 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: less than 90% ovicidal or larvicidal rate As a result, the following compounds showed a. (1), (2), (3), (4), (6), (8), (10), (11), (1
2), (13), (14), (43), (57), (88) The non-treated section was c. Test Example 3 (Insecticidal test against brown planthopper larvae) 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, put rice stalks in a 5.5 cm diameter polyethylene cup lined with 5.5 cm diameter filter paper containing 1 ml of water, and release about 30 larvae of the brown planthopper into the cup. investigated. The criteria for effect evaluation are: a: No live insects are observed. b: Five or less surviving insects are recognized. c: 〃 6 or more are allowed. And As a result, the following compounds showed a. (4), (6), (7), (9), (12) In addition, the untreated plot shows 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 (50 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 criteria for effect evaluation were as follows: a: 100% mortality rate b: 99-90% mortality rate c: less than 90% mortality rate. As a result, the following compounds showed a. (1), (2), (3), (4), (6), (7), (8), (9), (1
0), (11), (12), (13), (14), (15), (28), (57) The non-treated section is c.

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 following compounds showed a mortality rate of 80% or more. (1), (2), (3), (7), (8), (11), (12), (13), (1
5) In addition, no treatment showed a mortality rate 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, the following compounds showed 100% mortality. (1), (2), (4), (5), (6), (7), (9), (10), (1
1), (12), (13), (14), (15), (43), (57), (88) The untreated plot showed a mortality rate of 0%. Test Example 7 (Insecticidal test against Culex pipiens) A test compound was made into an emulsion in accordance with Formulation Example 1, diluted with water, and 0.7 ml of the solution was added to 100 ml of ion-exchanged water.
(Active ingredient concentration 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 following compounds showed a. (1 2 3 4 5 6 7 8) ,
(9), (10), (11), (12), (13), (14), (15), (28), (5
7), (88) Test Example 8 (Insecticidal test against cotton aphid) About 20 cotton aphid larvae were parasitized on cotton (primary leaf developing stage) planted in a polyethylene cup, and an emulsion was prepared in accordance with Formulation Example 1. 30 ml of a diluted solution of the test compound in water (active ingredient concentration 50 ppm) was sprayed per pot. The number of surviving insects was counted 7 days after the treatment, and the control value was determined by comparison with the number of surviving untreated insects. As a result, compound (1) showed a control value of 98.7%. Compound A showed a control value of 57.3%.

Test Example 9 Mouse Oral Acute Toxicity Test Each of the test compounds was diluted to a predetermined concentration with corn oil,
About 20 ICR 6-week-old male mice (weight 24-31 g)
Diluted solution 0.1g per 10g body weight after fasting
Each ml was forcibly administered intragastrically. Four hours after the administration, food and water were given and the animals were kept in cages. Seven days after the administration, the life and death were investigated and the mortality rate was calculated (5 animals per group). The results are shown in Table 9.

[Table 9]

[0023]

The compounds of the present invention show excellent insecticidal efficacy,
Acute toxicity to mammals is also relatively low.

Front page continuation (72) Inventor Hiroshi Kishida 4-2-1 Takashi Takarazuka-shi, Hyogo Prefecture Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Shigeru Saito 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Kagaku Industry Co., Ltd.

Claims (8)

[Claims] 1. A general formula: ## STR1 ## [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a methoxymethyl group or a cyanomethyl group. However, R ¹ and R ² are not hydrogen atoms at the same time. R ³
Represents a trifluoromethyl group or a methyl group, and X represents a halogen atom. ] The hydrazone compound represented by these. 2. The hydrazone compound according to claim 1, wherein R ³ is a trifluoromethyl group. 3. The hydrazone compound according to claim 2, wherein X is a chlorine atom. 4. 4-Chloro-4 ′-(trifluoromethylsulfonyloxy) benzophenone-N ′, N′-diacetylhydrazone. 5. A 4-chloro-4 ′-(trifluoromethylsulfonyloxy) benzophenone-N ′, N′-di (ethoxycarbonyl) hydrazone. 6. A 4-chloro-4 ′-(trifluoromethylsulfonyloxy) benzophenone-N ′, N′-di (methoxyacetyl) hydrazone. 7. 4-Chloro-4 '-(trifluoromethylsulfonyloxy) benzophenone-N', N'-di (cyanomethyl) hydrazone. 8. An insecticide containing the hydrazone compound according to claim 1 as an active ingredient.