JP2879174B2 - Hydrazone derivatives, their production, their uses and their use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound of the formula (I) (Wherein, R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a lower alkyl group; X may be the same or different; a halogen atom, a nitro group, a lower alkyl A lower haloalkyl group, a lower alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group or a lower alkylsulfonyl group, Y may be the same or different, and a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl Group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower alkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylthio group, lower haloalkylsulfinyl group, lower haloalkylsulfonyl group, lower alkynyl group or lower alkoxycarbonyl group , Z may be the same or different, and , Nitro group, cyano group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkylsulfinyl group, lower haloalkylsulfinyl group, lower alkylsulfonyl group, lower haloalkyl It represents a sulfonyl group, a lower haloalkylsulfonyloxy group, a lower alkylcarbonyl group or a phenoxy group, and l, m and n each represent an integer of 0 to 5.)
The present invention relates to a hydrazone derivative represented by the formula:

[0002]

2. Description of the Related Art JP-A-48-91223 and JP-A-54
Hydrazones are disclosed as insecticides and pesticides in JP-A-122261, JP-A-56-45452, JP-A-63-93761, and the like.

The inventors of the present invention have conducted intensive studies to create a novel insecticide. As a result, the hydrazone derivative represented by the general formula (I) has been described or suggested in the prior art literature or the like. The present invention has been found to be a novel compound which has not been described, and which has not been described in the literature, and has an excellent insecticidal effect at a low dose, and has completed the present invention.

[0003]

Means for Solving the Problems A typical method for producing the hydrazone derivative represented by the general formula (I) of the present invention includes:
For example, it can be manufactured by the manufacturing method shown below. (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X, Y, Z, 1, m and n are the same as described above.) The compound represented by the general formula (III) and the general formula (III) The aniline represented by the formula (II) is reacted in the presence of an inert solvent, in the presence or absence of a base and / or a condensing agent, or is reacted with the general formula (I
A hydrazone derivative represented by the general formula (I) can be produced by reacting a compound represented by the formula (V) with a halide represented by the general formula (V) in the presence of an inert solvent and a base. it can.

[0004] 1. General formula (III) → General formula (I) As the inert solvent that can be used in this reaction, any solvent that does not significantly inhibit the progress of this reaction may be used.Examples include halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride. , Aromatic hydrocarbons such as benzene, toluene and xylene; nitriles such as acetonitrile and benzonitrile; and chain ethers such as methylcellosolve and diethyl ether.
Cyclic ethers such as ters, dioxane, tetrahydrofuran, etc.
Ketones such as ters, acetone, methyl ethyl ketone,
Esters such as ethyl acetate, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO),
Pyridine and the like can be exemplified, and these inert solvents may be used alone or in combination. As the base used in this reaction, an organic base or an inorganic base can be used.Examples of the inorganic base include hydroxides or carbonates of alkali metal atoms such as sodium and potassium, and alkaline earth metal atoms such as calcium and magnesium. Salts, hydrides of alkali metal atoms such as sodium hydride, and organic bases such as triethylamine, pyridine, N, N-dimethylaniline, 2,6-dimethylpyridine, 4-N, N-dimethylaminopyridine and the like are used. The amount thereof can be selected from the range of the amount of the catalyst or from the equimolar amount to the excess molar amount with respect to the compound represented by the general formula (III).

As the condensing agent, for example, carbodiimidazole, dicyclohexylcarbodiimide, 2-chloro-1-methylpyridinium iodide and the like can be used, the amount of which is represented by the general formula (III) May be used by selecting from a range of equimolar to excess molar. Since this reaction is an equimolar reaction, each reactant may be used in an equimolar amount, but an aniline may be used in excess. The reaction temperature may be appropriately selected from the range of room temperature to the boiling point range of the inert solvent to be used, and the reaction is preferably carried out under heating. The reaction time is not fixed depending on the reaction amount, the reaction temperature and the like, but may be selected from a range of several minutes to 48 hours. After completion of the reaction, the reaction solution containing the target substance is subjected to a conventional method, for example, solvent distillation, solvent extraction, and the like, and if necessary, a recrystallization method,
The target product can be produced by purification by column chromatography or the like.

[0006] 2. General formula (IV) → General formula (I) The compound represented by general formula (IV) is reacted with a halide represented by general formula (V) in the presence of an inert solvent and a base to form a compound represented by general formula (IV). The hydrazone derivative represented by (I) can be produced. The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include alcohols such as methanol, ethanol, and propanol, dichloromethane, chloroform, and tetrachloride. Halogenated hydrocarbons such as carbon, benzene, toluene, aromatic hydrocarbons such as xylene, acetonitrile,
Nitriles such as benzonitrile, chain ethers such as methyl cellosolve and diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran, ketones such as acetone, esters such as ethyl acetate, dimethylformamide, dimethyl Acetamide, dimethyl sulfoxide, water and the like can be exemplified. These inert solvents may be used alone or in combination. As the base used in this reaction, an organic base or an inorganic base can be used.Examples of the inorganic base include hydroxides or carbonates of alkali metal atoms such as sodium and potassium, and alkaline earth metal atoms such as calcium and magnesium. Salts, hydrides of alkali metal atoms such as sodium hydride, organic bases include sodium methoxide, alkali metal alcoholates such as potassium t-butoxide, aluminides of alkali metal atoms such as sodium amine, triethylamine And the like. Tertiary alkylamines such as pyridine, 4-N, N-dimethylaminopyridine and the like can be used.

The amount of the base used may be selected from the range of equimolar to excess molar with respect to the compound represented by the general formula (IV). Since this reaction is an equimolar reaction, each reactant may be used in an equimolar amount, but the halides represented by the general formula (V) may be used in excess. The reaction temperature may be appropriately selected from the range from room temperature to the boiling point range of the inert solvent used. The reaction time is not fixed depending on the reaction amount, the reaction temperature and the like, but may be selected from a range of several minutes to 48 hours. After completion of the reaction, the target product can be produced in the same manner as in the above reaction. The compound represented by the general formula (III), which is a raw material compound for producing the hydrazone derivative represented by the general formula (I) of the present invention, is disclosed in JP-A-62-2223169 and JP-A-64-223169.
-70462, J. Org. Chem., 417 (1941), Ber. 56B, 10
60-1065 (1923). The compound represented by the general formula (IV) is Collection Cz
ech. Chem. Communs., 25, 261-2667 (1960). The general formula of the present invention is shown below.
(I) is exemplified in Table 1, but the present invention is not limited to these compounds.

General formula (I) (Below)

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

In Table 1, NMR data of the paste-like material are shown in Table 2. Hereinafter, typical examples of the present invention will be described, but the present invention is not limited thereto.

Embodiment 1 1-1 . 2- [N- (4-cyanobenzyl) -N-
Production of (3-trifluoromethylphenyl)] hydrazonoacetic acid 13.46 3-trifluoromethylphenylhydrazine
g (76.5 mmol) in 100 ml of toluene,
8.12 g (80.4 mmol) of triethylamine and 14.99 g (76.5 mmol) of 4-cyanobenzyl bromide were added, and the reaction was carried out under heating for 3 hours. After completion of the reaction, the reaction solution was washed with water (50 ml × 2), and the organic layer was concentrated.
Then, the concentrate was dissolved in 80 ml of ethanol, and
11.51 g (62.2 mmol) of a 0% glyoxylic acid aqueous solution was added dropwise, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the solvent was distilled off from the reaction solution containing the target substance, and water 50
The mixture was extracted with ethyl acetate (100 ml × 2), the extract was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the precipitated crystals were washed with a hexane-ether mixed solution.
3.02 g of the desired product was obtained. Physical properties: mp 220 ° C Yield 60.2%

1-2 . Production of 2- [N- (4-cyanobenzyl) -N- (3-trifluoromethylphenyl)] hydrazono 4-chloroacetanilide (Compound No.
39) 2- [N- (4-cyanobenzyl)-obtained in 1-1.
[N- (3-trifluoromethylphenyl)] hydrazonoacetic acid (0.59 g, 1.7 mmol) was suspended in 7 ml of carbon tetrachloride, 0.40 g (3.4 mmol) of thionyl chloride was added, and the mixture was heated for 1.5 hours. Refluxed. After completion of the reaction, the reaction solvent was distilled off under reduced pressure, and the acid chloride obtained was dissolved in 10 ml of tetrahydrofuran with 0.62 g (1.7 mmol) of 4-chloroaniline and 0.37 g (3.7 mmol) of triethylamine. The mixture was stirred at room temperature for 1 hour. After completion of the reaction, 10 ml of water was added to the reaction solution, and the desired product was extracted with ethyl acetate (100 ml × 2). The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 0.51 g of the desired product. Physical properties mp 164-165 ° C Yield 65.0%.

Example 2 2- [N- (3-chlorophenyl) -N- (4-cyanobenzyl)] hydrazono 4-
Production of trifluoromethoxyacetanilide (Compound N
o. 22) 1.50 g (4.8 mmol) of 2- [N- (3-chlorophenyl) -N- (4-cyanobenzyl)] hydrazonoacetic acid prepared in the same manner as in 1-1, 2-chloro-iodide
1.34 g (5.3 mmol) of 1-methylpyridinium, 0.85 g of 4-trifluoromethoxyaniline
(4.8 mmol) was dissolved in 20 ml of pyridine and heated under reflux for 3 hours. After completion of the reaction, the solvent was distilled off, 30 ml of water was added, and the desired product was extracted with ethyl acetate (50 ml × 2). The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure.
The obtained residue is subjected to silica gel column chromatography.
(Hexane-ethyl acetate) to give 1.64 g of the desired product. Physical properties mp 160.5-162.0 ° C Yield 72.
3%.

Example 3 2- [N- (4-chlorophenyl) -N- (4-nitrobenzyl)] hydrazono 4-
Production of trifluoromethoxyacetanilide (Compound N
o. 28) 1.30 g (3.9 mmol) of 2- [N- (4-chlorophenyl) -N- (4-nitrobenzyl)] hydrazonoacetic acid and 0.63 g of carbonyldiimidazole prepared in the same manner as in 1-1. (3.9 mmol) was dissolved in 10 ml of tetrahydrofuran and stirred at room temperature for 5 hours.
After completion of the reaction, 30 ml of water was added and ethyl acetate (50 ml ×
Extract in 2), dry the extract with anhydrous sodium sulfate,
The residue obtained by concentration under reduced pressure was dissolved in 20 ml of pyridine, and 0.69 g of 4-trifluoromethoxyaniline was dissolved.
(3.9 mmol) and 0.10 g (0.8 mmol) of 4-dimethylaminopyridine were added, and the mixture was stirred under heating and reflux for 12 hours. After completion of the reaction, the solvent is distilled off and water 3
0 ml was added, the desired product was extracted with ethyl acetate (50 ml × 2), the extract was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue obtained was subjected to silica gel column chromatography (hexane-ethyl acetate). Purification yielded 0.95 g of the desired product. Physical properties mp 111.0-115.1 ° C. Yield 49.
5%.

Embodiment 4 4-1 . Production of 2-phenylhydrazono 4-trifluoromethoxyacetanilide 30.24 g (0.28 mol) of phenylhydrazine was dissolved in 200 ml of ethanol, 51.80 g (0.28 mol) of a 40% aqueous glyoxylic acid solution was added dropwise under ice cooling, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the precipitated crystals were washed with a hexane-ether mixed solution to obtain 20.2 g of phenylhydrazonoacetic acid (43.9% yield). A solution of 7.81 g (47.6 mmol) of the obtained phenylhydrazonoacetic acid and 10.58 g (104.7 mmol) of triethylamine in 30 ml of dichloromethane was added to 2-chloro-1 iodide.
12.17 g (47.6 mmol) of -methylpyridinium and 8.43 g of 4-trifluoromethoxyaniline
(47.6 mmol) was added dropwise to a solution of 100 ml of dichloromethane and stirred at room temperature for 5 hours. After completion of the reaction, the solvent was distilled off, 50 ml of water was added, the desired product was extracted with ethyl acetate (100 ml × 2), the extract was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane-ethyl acetate) gave 7.62 g of the desired product. Physical properties mp 151.2-154.3 ° C Yield 49.
6%.

4-2 . tert-butyl 4- [2-
Production of (4-trifluoromethoxyphenylcarbamoylmethyl-N-phenylhydrazono-N-methyl) benzoic acid (Compound No. 11) 0.71 g (2.2 mmol) of phenylhydrazono 4-trifluoromethoxyacetanilide obtained in 4-1 was dissolved in 20 ml of dimethylformamide, and 0.27 g (2.4 mmol) of potassium tert-butoxide was cooled with ice. And tert-butyl 4-chloromethylbenzoic acid.
54 g was added, and the reaction was carried out at room temperature for 3 hours. After the completion of the reaction, 50 ml of ice water was added, and the desired product was treated with ethyl acetate (100 ml).
× 2), the extract was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 0.70 g of the desired product. Was. Physical properties mp 142.2-143.7 ° C Yield 70.
0%.

The agricultural and horticultural insecticides containing the hydrazone derivative represented by the general formula (I) of the present invention as an active ingredient include rice, vegetables,
It is suitable for pest control such as various agriculture and forestry, horticulture, storage pests, sanitary pests, nematodes and the like which inflict fruit trees, other crops and flowers. For example, adoxophyes
orana fasciata)
phyes sp.), apple squirrel (Grapholita inopina)
ta), Nashihime Singa (Grapholita mlesta), Mameshin Singing (Leguminivora glycinivorella), Kuwamaki (Olethreutes mori), Canohosoga (Caloptil)
ia thevivora), apple hosoga (Caloptilia zachrysa)
), Kinmonhosoga (Phyllonorycterringoniella)
), Pear squirrel (Spulerina astaurota), white butterfly (Pie-rs rapae crucivora), giant tobacco (Heliothis sp.), Codling moth (L-aspeyresia pomon)
ella), diamondback moth (Plutella xylostella), apple squirrel (Argyresthia conjugella), peach squirrel (Carposina niponensis), squid (Chilo suppre)
ssalis, Coleoptera (Cnaphalocrocis medinali)
s), Chamodara moth (Ephestia elutella), Kuwanomeiga (Glyphodes pyloa-lis), Sankameiga (Sc)
irpophaga incertulas)
guttata), armyworm (Pseudaletia separata), rice armyworm (Sesamia i-nferens), lotus armyworm (Sp
Odoptera litura, Spodoptera litura (Spodopte)
ra exigua) and other lepidopteran pests, leafhopper leafhopper (Macr
osteles fasci-frons), leafhopper (Nephotet)
tix cincticeps), brown planthopper (N-ilaparvata lug)
ens), white-fed groundhopper (Sogatella furcifera), citrus whitefly (Diaphorina citri), grape whitefly (Aleurolobus taonabae), and tobacco whitefly (Bemisi)
a tabaci), Whiteflies (Trialeurodes vapor)
ari-orum), radish aphid (Lipaphis erysi)
mi), peach aphid (Myzus persicae), horned beetle (Ceroplastes ceriferus), citrus stag beetle (Pulvinaria aurantii), citrus red stalk (Pseudaonidiaduplex), pear stalk (Comstockaspis perniciosa), etc. Pterodactyl pests, Praty-lenchus sp.
a rufocuprea), Bean beetle (Popilliajaponica)
), Tobacco beetle (Lasioderma serricorne),
Flying bark beetle (Lyctus brunneus), Japanese beetle beetle (Epilachna vigintioctopu-nctata), adzuki beetle (Callosobruchus chinensis), beetle weevil (L-istroderes costirostris), weevil (Sitophilus zeomais)
grandis grandis), rice weevil (Lissorhoptru)
s o-ryzophilus, cricket beetle (Aulacophora femorali)
s), rice beetle (O-ulema oryzae), flea beetle (Phyllotreta striolata), weevil (Sitophilus zeamais), pine bark beetle (Tomicus)
piniperda, Colorado potatoes (Leptinotarsa)
decemlineata), Mexican beans (Epilac
hna varivestis), corn worms (Diabrotica)
sp.), beetles such as Coleoptera, sea flies (Dacus (Zeugodac
us) cucurbitae), Citrus fruit fly (Dac-us (Bactrocer)
a) dorsalis), rice leafhopper (Agromyza oryzae)
), Onion flies (Delia antiqua), flies (Del)
ia platura), soybean flies (Asphondylia sp.)
), Housefly (Musca domestica), Musca domestica (Cul)
ex p-ipiens pipiens), dipteran pests, Pratylenchu-s coffeae, potato cyst nematodes (Globodera rostochiensis), root-knot nematodes (Meloidogyne sp.), tangerine nematodes (Tylenchulus sem-ene) It also has an insecticidal effect against the nematodes of the order Nematodes (Aphelenchus avenae) and the nematodes (Aphelenchoides ritzemabosi), and particularly has a remarkable effect on insects such as Lepidoptera and Coleoptera. It is.
The scientific names are based on the 1987 Agricultural and Forestry Pests and Insects Directory (edited by the Japan Society of Applied Animal Entomology).

The agricultural and horticultural insecticide of the present invention has a remarkable insecticidal effect on the above-mentioned pests or sanitary pests that infect paddy fields, fruit trees, vegetables, other crops, flowers and the like. Before and after the occurrence of the pests is confirmed, the paddy fields, fruit trees, vegetables, other crops, paddy water such as flowers, foliage or soil, etc. The intended effect of the insecticide of the present invention can be obtained by treating the inside of a house or a ditch around a house where the occurrence of the above-mentioned pests or the occurrence of the above-mentioned pests is predicted. However, the present invention is not limited to only these embodiments. When the hydrazone derivative represented by the general formula (I) of the present invention is used as an agricultural and horticultural insecticide, it is generally used by formulating it into a convenient form according to a conventional method for pesticide formulation. is there. That is, the hydrazone derivatives of the present invention represented by the general formula (I) are dissolved, separated, suspended in a suitable inert carrier or, if necessary, together with an auxiliary in an appropriate ratio. It may be turbid, mixed, impregnated, adsorbed or adhered and formulated into an appropriate dosage form, for example, a suspension, emulsion, liquid, wettable powder, granule, powder, tablet or the like. The inert carrier that can be used in the present invention may be either solid or liquid. Examples of the material that can be a solid carrier include soybean flour, cereal flour, wood flour, bark flour, saw flour, and tobacco stem flour. , Walnut shell powder, bran, cellulose powder, residue after extraction of plant extract, synthetic polymers such as pulverized synthetic resins, clays (eg, kaolin, bentonite, acid clay), talcs (eg, talc, pyrophyllide, etc.), Silica (for example, diatomaceous earth, silica sand, mica, white carbon [a synthetic high-dispersion silicic acid which is also called hydrous finely divided silicon or hydrous silicic acid, and which contains calcium silicate as a main component depending on the product]), activated carbon, sulfur powder, Inorganic mineral powders such as pumice, calcined diatomaceous earth, crushed brick, fly ash, sand, calcium carbonate, calcium phosphate, ammonium sulfate,
Examples include chemical fertilizers such as phosphorous, nitrate, urea, and salt, and composts, and these are used alone or in the form of a mixture of two or more.

The material which can be a liquid carrier is selected from those having a solvent function per se, and those capable of dispersing the active ingredient compound with the aid of an auxiliary even without the solvent function. The following carriers can be exemplified as typical examples. These can be used alone or in the form of a mixture of two or more. Examples thereof include water, alcohols (eg, methanol, ethanol, isopropanol, butanol). , Ethylene glycol and the like), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Diisobutyl ketone, cyclohexanone, etc.), ethers (eg, ethyl ether, dioxane, cellosolve,
Dipropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, kerosene, mineral oil, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, alkylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloroethane) , Chloroform, carbon tetrachloride, chlorinated benzene, etc.), esters (eg, ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctophthalate), amides (eg, dimethylformamide, diethylformamide, dimethylacetamide) Etc.), nitriles (eg, acetonitrile, etc.), dimethyl sulfoxides and the like. Examples of the other adjuvants include the following representative adjuvants. These adjuvants are used according to the purpose, and may be used alone or in combination of two or more kinds. In some cases, it is possible to use no auxiliaries at all.

Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compounds, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene, and the like. Ethylene higher fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkyl aryl sulfonate, naphthalene sulfonic acid condensate,
Surfactants such as lignin sulfonate and higher alcohol sulfate can be exemplified. For the purpose of stabilizing the dispersion of the active ingredient compound, adhering and / or binding, the following auxiliaries can be used. For example, casein, gelatin, starch, methylcellulose, carboxymethylcellulose can be used. Auxiliaries such as gum arabic, polyvinyl alcohol, pine oil, bran oil, bentonite, and lignin sulfonate can also be used. The following auxiliaries can be used to improve the flowability of the solid product. For example, auxiliaries such as wax, stearate, alkyl phosphate and the like can be used. As peptizers for suspension products, auxiliary agents such as, for example, naphthalenesulfonic acid condensates, condensed phosphates and the like can also be used. As an antifoaming agent, for example, an auxiliary agent such as silicone oil can be used.

The compounding ratio of the active ingredient compound can be adjusted according to need. For example, 0.01 to 50% by weight in the case of powder or granules, and 0.1% in the case of emulsion or wettable powder. A suitable amount is from 01 to 50% by weight. The agricultural and horticultural insecticide containing the hydrazone derivative represented by the general formula (I) of the present invention as an active ingredient is used as it is, or is appropriately diluted or suspended with water or the like in order to control various pests. An effective amount for controlling the pest may be applied to the pest or a place where the generation or growth of the pest is not preferable. The amount of the agricultural and horticultural insecticide containing the hydrazone derivative represented by the general formula (I) of the present invention as an active ingredient depends on various factors, for example, the purpose, the target pest, the growth status of the crop, the pest occurrence tendency, the weather, Environmental conditions, dosage forms, application methods, application locations,
Although it varies depending on the application time, etc., 1
It may be appropriately selected from the range of 0.1 g to 5 kg per 0 arc depending on the purpose. Agricultural and horticultural insecticides containing the hydrazone derivative represented by the general formula (I) of the present invention as an active ingredient are further used as pests to be controlled, other insecticides for the purpose of extending the suitable period of control, or for reducing the amount of drugs. Alternatively, it can be used in combination with a bactericide. Hereinafter, typical formulation examples and test examples of the present invention are shown, but the present invention is not limited thereto. In addition, in the formulation examples, "parts" indicates parts by weight.

Formulation Example 1 Compound of the present invention 50 parts Xylene 40 parts Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 10 parts The above are uniformly mixed and dissolved to form an emulsion. Formulation Example 2 Compound of the present invention 3 parts Clay powder 82 parts Diatomaceous earth powder 15 parts The above are uniformly mixed and pulverized to give a powder. Formulation Example 3 Compound of the present invention 5 parts Mixed powder of bentonite and clay 90 parts Calcium ligninsulfonate 5 parts The above components were uniformly mixed, kneaded by adding an appropriate amount of water, and granulated.
Dry to granules. Formulation Example 4 Compound of the present invention 20 parts Kaolin and synthetic highly dispersed silicic acid 75 parts Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 5 parts The above are uniformly mixed and pulverized to obtain a wettable powder.

Test Example 1 Spodoptera
Insecticidal test on litura ) Cabbage leaf pieces (variety: four seasons harvest) were immersed for about 30 seconds in a drug solution prepared by diluting a drug containing the compound of the present invention as an active ingredient to 500 ppm. After air-drying, it was placed in a plastic dish having a diameter of 9 cm, inoculated with the second instar larvae of Spodoptera litura, covered, and allowed to stand in a constant temperature room at 25 ° C. Eight days after the inoculation, the number of live and dead insects was investigated, the mortality was calculated by the following formula, and judgment was made according to the following criteria. 10 units in 1 ward, 3 consecutive

(Equation 1) Judgment criteria. A: 100% mortality B: 99% to 90% mortality C: 89% to 80% mortality D: 79% to 50% mortality Table 3 Shown in

[0023]

Test Example 2 Sitophilus zeam
a ) Insecticidal test against adult insects Brown rice was immersed for about 30 seconds in a drug solution obtained by diluting a drug containing the compound of the present invention as an active ingredient to 200 ppm. Diameter 4 after air drying
After placing in a glass dish of cm and inoculating adult black elephants, it was covered and left to stand in a constant temperature room at 25 ° C. Eight days after the inoculation, the number of live and dead insects was examined, and the mortality was calculated according to Test Example 1. 10 units per ward in three wards. The results are shown in Table 4.

[0024]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 249/16 C07C 249/16 255/60 255/60 255/66 255/66 317/32 317/32 317/34 317/34 323/41 323/41 323/48 323/48 // A01N 25/04 101 A01N 25/04 101 (56) References JP-B-45-10519 (JP, B1) (58) Fields surveyed (Int.Cl . ^6, DB name) C07C 251/74 A01N 37/18 A01N 37/34 A01N 41/04 A01N 41/10 C07C 249/16 C07C 255/60 C07C 255/66 C07C 317/32 C07C 317/34 C07C 323/41 C07C 323/48 CA (STN) REGISTRY (STN)

Claims (15)

(57) [Claims] (1) General formula (I) (Wherein, R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a lower alkyl group; X may be the same or different; a halogen atom, a nitro group, a lower alkyl A lower haloalkyl group, a lower alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group or a lower alkylsulfonyl group, Y may be the same or different, and a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl Group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower alkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylthio group, lower haloalkylsulfinyl group, lower haloalkylsulfonyl group, lower alkynyl group or lower alkoxycarbonyl group , Z may be the same or different, and , Nitro group, cyano group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkylsulfinyl group, lower haloalkylsulfinyl group, lower alkylsulfonyl group, lower haloalkyl It represents a sulfonyl group, a lower haloalkylsulfonyloxy group, a lower alkylcarbonyl group or a phenoxy group, and l, m and n each represent an integer of 0 to 5.)
A hydrazone derivative represented by 2. In the general formula (I), R ¹ , R ² , R ³ and R ⁴
May be the same or different, represents a hydrogen atom or a lower alkyl group, X may be the same or different, represents a halogen atom, a lower alkyl group, or a lower haloalkyl group;
Y may be the same or different and represents a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower haloalkylthio group or a lower haloalkylsulfinyl group;
May be the same or different, a halogen atom, a nitro group,
A cyano group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or a lower haloalkoxy group;
The hydrazone derivative according to claim 1, wherein each of n and n represents an integer of 0 to 3. 3. In the general formula (I), R ¹ , R ² , R ³ and R ⁴
May be the same or different and represents a hydrogen atom or a lower alkyl group; X may be the same or different and represents a halogen atom, a lower alkyl group or a lower haloalkyl group;
May be the same or different, represents a cyano group, a nitro group or a lower haloalkylsulfinyl group, Z may be the same or different, represents a halogen atom, a lower haloalkyl group or a lower haloalkoxy group, and l, m and n represent Each one
The hydrazone derivative according to claim 2, which represents an integer of 3. 4. The compound according to claim 3, wherein in formula (I), at least one X is substituted at the 3-position, at least one Y is substituted at the 4-position, and at least one Z is substituted at the 4-position. Hydrazone derivatives. 5. A compound of the general formula (III) (Wherein, R ¹ , R ² and R ³ may be the same or different and each represent a hydrogen atom or a lower alkyl group; R ⁵ represents a halogen atom or a hydroxyl group; X may be the same or different; A nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group or a lower alkylsulfonyl group, Y may be the same or different, a halogen atom, a cyano group, a nitro group, Lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower alkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylthio group, lower haloalkylsulfinyl group, lower haloalkylsulfonyl group, lower alkynyl group or Represents a lower alkoxycarbonyl group, and l and m are each Represents an integer of 0 to 5. The compound represented by) the formula (II) (Wherein, R ⁴ represents a hydrogen atom or a lower alkyl group; Z may be the same or different; a halogen atom, a nitro group, a cyano group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group) A lower alkylthio group, a lower haloalkylthio group, a lower alkylsulfinyl group, a lower haloalkylsulfinyl group, a lower alkylsulfonyl group, a lower haloalkylsulfonyl group, a lower haloalkylsulfonyloxy group, a lower alkylcarbonyl group or a phenoxy group; A general formula (I) characterized by reacting with an aniline represented by the formula: (Wherein, R ¹ , R ² , R ³ , R ⁴ , X, Y, Z, 1, m, and n are the same as described above). 6. Formula (IV) (Wherein, R ³ and R ⁴ may be the same or different and each represent a hydrogen atom or a lower alkyl group; X may be the same or different; and a halogen atom, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower Represents an alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group or a lower alkylsulfonyl group, Z may be the same or different, and a halogen atom, a nitro group, a cyano group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower Haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkylsulfinyl group, lower haloalkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylsulfonyl group, lower haloalkylsulfonyloxy group,
A lower alkylcarbonyl group or a phenoxy group,
And n each represent an integer of 0 to 5. ) And the general formula (V) (Wherein, R ¹ and R ² may be the same or different and each represent a hydrogen atom or a lower alkyl group; Y may be the same or different; a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl Group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower alkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylthio group, lower haloalkylsulfinyl group, lower haloalkylsulfonyl group, lower alkynyl group or lower alkoxycarbonyl group , M represents an integer of 0 to 5, and Hal represents a halogen atom.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , X, Y, Z, 1, m, and n
Is the same as above. )). 7. The formula (I) (Wherein, R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a lower alkyl group; X may be the same or different; a halogen atom, a nitro group, a lower alkyl A lower haloalkyl group, a lower alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group or a lower alkylsulfonyl group, Y may be the same or different, and a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl Group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower alkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylthio group, lower haloalkylsulfinyl group, lower haloalkylsulfonyl group, lower alkynyl group or lower alkoxycarbonyl group , Z may be the same or different, and , Nitro group, cyano group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkylsulfinyl group, lower haloalkylsulfinyl group, lower alkylsulfonyl group, lower haloalkyl It represents a sulfonyl group, a lower haloalkylsulfonyloxy group, a lower alkylcarbonyl group or a phenoxy group, and l, m and n each represent an integer of 0 to 5.)
A pesticide for agricultural and horticultural use, characterized by containing a hydrazone derivative represented by the following as an active ingredient. 8. In the general formula (I), R ¹ , R ² , R ³ and R ⁴
May be the same or different, represents a hydrogen atom or a lower alkyl group, X may be the same or different, represents a halogen atom, a lower alkyl group, or a lower haloalkyl group;
Y may be the same or different and represents a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower haloalkylthio group or a lower haloalkylsulfinyl group;
May be the same or different, a halogen atom, a nitro group,
A cyano group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or a lower haloalkoxy group;
The agricultural and horticultural insecticide according to claim 7, wherein each of n and n represents an integer of 0 to 3. 9. In the general formula (I), R ¹ , R ² , R ³ and R ⁴
May be the same or different and represents a hydrogen atom or a lower alkyl group; X may be the same or different and represents a halogen atom, a lower alkyl group or a lower haloalkyl group;
May be the same or different, represents a cyano group, a nitro group or a lower haloalkylsulfinyl group, Z may be the same or different, represents a halogen atom, a lower haloalkyl group or a lower haloalkoxy group, and l, m and n represent Each one
9. The insecticide for agricultural and horticultural use according to claim 8, which represents an integer of 3. 10. In the general formula (I), at least one X is substituted at the 3-position, at least one Y is substituted at the 4-position, and at least one Z is substituted at the 4-position. Agricultural and horticultural insecticides according to Item. 11. Formula (I) for controlling useful crops from unwanted pests (Wherein, R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a lower alkyl group; X may be the same or different; a halogen atom, a nitro group, a lower alkyl A lower haloalkyl group, a lower alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group or a lower alkylsulfonyl group, Y may be the same or different, and a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl Group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower alkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylthio group, lower haloalkylsulfinyl group, lower haloalkylsulfonyl group, lower alkynyl group or lower alkoxycarbonyl group , Z may be the same or different, and , Nitro group, cyano group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkylsulfinyl group, lower haloalkylsulfinyl group, lower alkylsulfonyl group, lower haloalkyl It represents a sulfonyl group, a lower haloalkylsulfonyloxy group, a lower alkylcarbonyl group or a phenoxy group, and l, m and n each represent an integer of 0 to 5.)
An agricultural and horticultural insecticide containing as an active ingredient a hydrazone derivative represented by
A method for controlling unwanted pests, characterized in that the treatment is carried out at a dose of g to 5 kg. 12. In the general formula (I), R ¹ , R ² , R ³ and
R ⁴ may be the same or different, represents a hydrogen atom or a lower alkyl group, X may be the same or different, represents a halogen atom, a lower alkyl group, or a lower haloalkyl group;
Y may be the same or different and represents a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower haloalkylthio group or a lower haloalkylsulfinyl group;
May be the same or different, a halogen atom, a nitro group,
A cyano group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or a lower haloalkoxy group;
The control method according to claim 11, wherein each of n and n represents an integer of 0 to 3. 13. In the general formula (I), R ¹ , R ² , R ³ and
R ⁴ may be the same or different, represents a hydrogen atom or a lower alkyl group, X may be the same or different, represents a halogen atom, a lower alkyl group or a lower haloalkyl group, Y
May be the same or different, represents a cyano group, a nitro group or a lower haloalkylsulfinyl group, Z may be the same or different, represents a halogen atom, a lower haloalkyl group or a lower haloalkoxy group, and l, m and n represent Each one
13. The control method according to claim 12, wherein the control method represents an integer of 3. 14. In the general formula (I), at least one X is substituted at the 3-position, at least one Y is substituted at the 4-position, and at least one Z is substituted at the 4-position.
The control method described in the section. 15. The control method according to claim 14, wherein the pest is a lepidopteran pest or a Coleoptera pest.