JPH0532603A - Hydrazine derivative, its production, use and usage - Google Patents

Abstract

PURPOSE:To obtain a new hydrazine derivative having excellent insecticidal effects with a small amount of aipplication. CONSTITUTION:A hydrazine derivative, e.g. 2-[N-(4-cyanobenzyl)-N-(3- trifluoromethylphenyl)]hydrazino-4-chloroacetanilide expressed by formula I (R<1> to R<4> are H or alkyl; X us halogen, nmtro, alkyl, haloalkyl, alkoxy, alkylthio, etc.; Y is halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl, etc.; Z is halogen, nitro, cyano, alkyl, phenoxy, etc.; l, m and n are 0-5). The above-mentioned compound expressed by formula I is obtained by reacting hydrazones expressed by formula II with a reducing agent.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the general formula (I)

[Chemical 6] (In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different,
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 alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group or a lower alkylsulfonyl group And Y may be the same or different, and is a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group. , A lower haloalkylthio group, a lower haloalkylsulfinyl group, a lower haloalkylsulfonyl group, a lower alkynyl group or a lower alkoxycarbonyl group, Z may be the same or different, and a halogen atom, a nitro group, a cyano group, a lower alkyl group, a lower alkyl group, Halo Archi Group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkylsulfinyl group, lower haloalkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylsulfonyl group, lower haloalkylsulfonyloxy group, lower alkylcarbonyl group Or a phenoxy group, and 1, m and n each represent an integer of 0 to 5) and a method for producing the same.
It relates to applications and usages.

[0002]

BACKGROUND OF THE INVENTION Insecticides and pesticides composed of hydrazine derivatives are disclosed, for example, in JP-A-48-91223 and JP-A-54-923.
-122261, 56-45452 and 63-
It is disclosed in Japanese Patent No. 93761.

[0003]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive studies conducted by the present inventors to provide a more useful insecticide,
The present invention has been completed by finding that the hydrazine derivative represented by the general formula (I) is a novel compound which has not been described in the literature and has an excellent insecticidal effect at a low application rate.

[0004]

A typical method for producing the hydrazine derivative represented by the general formula (I) of the present invention is as follows:
For example, the method illustrated below can be used.

[Chemical 7] (In the formula, R ¹ , R ² , R ³ , R ⁴ , X, Y, Z, 1, m and n are the same as above.) That is, the hydrazone represented by the general formula (II) is used as a reducing agent. By the reduction reaction in the presence of the general formula
The hydrazine derivative represented by (I) can be produced.

This reduction reaction can be carried out by catalytic reduction in the presence of a suitable reducing agent or catalyst. In the reaction using a reducing agent, for example, a reducing agent such as NaBH ₃ CN or NaBH ₄ can be used. . The amount of the reducing agent used may be selected from the equimolar to excess molar range in terms of the number of hydrides of the reducing agent with respect to the hydrazone represented by the general formula (II).

As the inert solvent which can be used in this reaction,
Any substance that does not significantly inhibit the progress of this reaction may be used, such as methanol, ethanol, propanol, butanol.
Alcohols such as alcohol, chain ethers such as diethyl ether, dioxane, cyclic ethers such as tetrahydrofuran, cellosolves such as methyl cellosolve, esters such as acetic acid ethyl ester, benzene, toluene, Aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, diglyme,
Examples thereof include dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, water, etc. These inert solvents may be used alone or in a mixture.

This reaction has a pH of 1 to 7 under acidic or neutral conditions.
The pH is preferably in the range of 4 to 6,
It may be adjusted by adding hydrogen chloride, hydrogen bromide or the like to the reaction system. The reaction temperature may be appropriately selected from the range of -20 ° C to the boiling point range of the inert solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., but is in the range of several minutes to 48 hours. After completion of the reaction, a desired product can be produced by subjecting the reaction solution containing the desired product to a conventional method, for example, distilling off the solvent, solvent extraction, etc., and optionally purifying by a recrystallization method, a column chromatography method or the like. it can.

Next, when catalytic reduction is carried out as a reduction reaction,
For example, it may be carried out according to a conventional method described in "New Experimental Chemistry Course" (Vol. 15-II: Maruzen) and the like. For example, usable inert solvents are, for example, methanol, ethanol, propanol and butanol. Alcohols such as alcohols, cellosolves such as methyl cellosolve, dioxane, cyclic ethers such as tetrahydrofuran, hydrocarbons such as hexane and cyclohexane, fatty acids such as acetic acid and ethyl acetate, or esters thereof, N, N-dimethylformamide, 1,3
Examples thereof include amides such as -dimethyl-2-imidazolidinone and N-methylpyrrolidone. These inert solvents may be used alone or in a mixture.

Examples of the catalyst used in this reaction include palladium carbon, palladium black, platinum dioxide,
A typical catalytic reduction catalyst such as Raney-Nickel can be used, and the amount thereof is appropriately selected from the range of 0.0001% to 20% by weight with respect to the hydrazone represented by the general formula (II). Just do it. The hydrogen pressure in this reaction is from normal pressure to 30.
It can be selected from the range of 0 atm, and is preferably in the range of normal pressure to 50 atm.

The reaction temperature may be appropriately selected from the range of room temperature to the boiling point range of the inert solvent used, preferably room temperature to 80 ° C. The reaction time varies depending on the reaction scale, reaction temperature, etc., but is in the range of several minutes to 80 hours. After completion of the reaction, the desired product can be produced by treating the reaction solution containing the desired product in the same manner as in the case of using a reducing agent.

The hydrazones represented by the general formula (II), which are the starting compounds for producing the hydrazone derivative represented by the general formula (I) of the present invention, can be produced by the following production method.

[Chemical 8] (In the formula, R ¹ , R ² , R ³ , R ⁴ , X, Y, Z, l, m and n are the same as defined above, and R ⁵ represents a hydroxyl group or a halogen atom,
Hal represents a halogen atom. )

The compound represented by the general formula (IV) and the general formula (II
I) is reacted with an aniline in the presence of an inert solvent, in the presence or absence of a base and / or a condensing agent, or the compound represented by the general formula (VI) and the general formula (V The hydrazone derivative represented by the general formula (II) can be produced by reacting the halide represented by the formula (1) with the presence of an inert solvent and a base.

The compounds represented by the general formula (IV) are disclosed in JP-A Nos. 62-223169 and 64-70462.
J. Org. Chem. , 417 (1941), 1941)
, Ber. 56B, 1060-1065 (1923)
And the like. General formula
The compound represented by (VI) is a Collection Cze.
ch. Chem. Communs. , 25,2651-
It can be produced by the method described in 2667 (1960).

Representative compounds of the hydrazine derivative represented by the general formula (I) of the present invention are shown in Table 1 below, but the present invention is not limited to these compounds.

[Chemical 9]

[Table 1] In Table 1, the NMR data of the paste-like physical properties are shown in Table 2.

[Table 2]

[0015]

EXAMPLES Representative examples of the present invention are shown below, but the present invention is not limited to these.

Example 1 1-1 . 2- [N- (4-cyanobenzyl) -N- (3
-Trifluoromethylphenyl)] hydrazonoacetic acid

[Chemical 10] 3-trifluoromethylphenylhydrazine 13.46
g (76.5 mmol) was dissolved in 100 ml of toluene,
Triethylamine (8.12 g, 80.4 mmol) and 4-cyanobenzyl bromide (14.99 g, 76.5 mmol) were added, and the reaction was carried out under heating for 3 hours. After the reaction was completed, 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 the solution was cooled with ice to 4 times.
11.51 g (62.2 mmol) of 0% aqueous glyoxylic acid 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 was added
ml was added, 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 and washed with 1
3.02 g of the desired product was obtained. Physical properties: melting point 220 ° C., yield 60.2%.

1-2 . Preparation of 2- [N- (4-cyanobenzyl) -N- (3-trifluoromethylphenyl)] hydrazono 4-chloroacetanilide

[Chemical 11] 2- [N- (4-cyanobenzyl) -obtained in 1-1
N- (3-trifluoromethylphenyl)] hydrazonoacetic acid (0.59 g, 1.7 mmol) was suspended in carbon tetrachloride (7 ml), thionyl chloride (0.40 g, 3.4 mmol) was added, and the mixture was heated for 1.5 hours. Refluxed. After the reaction was completed, the reaction solvent was distilled off under reduced pressure to obtain acid chloride, and 4-chloroaniline (0.62 g, 1.7 mmol) and triethylamine (0.37 g, 3.7 mmol) were dissolved in tetrahydrofuran (10 ml). The solution was added and stirred at room temperature for 1 hour. After completion of the reaction, 10 ml of water was added to the reaction solution, 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: melting point 164-165 ° C., yield 65.0
%.

1-3 . Preparation of 2- [N- (4-cyanobenzyl) -N- (3-trifluoromethylphenyl)] hydrazino 4-chloroacetanilide (Compound No. 27)

[Chemical 12] 2- [N- (4-cyanobenzyl) -obtained in 1-2
0.20 g (0.4 mmol) of N- (3-trifluoromethylphenyl)] hydrazono 4-chloroacetanilide was dissolved in a mixed solvent of 2 ml of tetrahydrofuran and 5 ml of methanol, and 0.10 g of sodium cyanoborohydride. (1.6 mmol) was added, and 0.7 ml of saturated hydrogen chloride methanol solution was added dropwise with stirring at room temperature, followed by stirring at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off, ethyl acetate was added, and the mixture was neutralized with aqueous sodium hydrogen carbonate. The ethyl acetate layer was separated, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate) to give 0.18.
g of the desired product was obtained. Physical properties: melting point 43 ° C., yield 89.2%.

Example 2 Preparation of 2- [N- (4-cyanobenzyl) -N- (3-trifluoromethylphenyl)] hydrazino 4-fluoromethoxyacetanilide (Compound No. 33)

[Chemical 13] 2- [N- (4-cyanobenzyl) -N- (3-trifluoromethylphenyl)] hydrazono 0.40 g (0.8 mmol) 4-trifluoromethoxyacetanilide in 3 ml of tetrahydrofuran and 7 ml of methanol. It was dissolved in a mixed solvent, 0.05 g (0.8 mmol) of sodium cyanoborohydride was added, 0.5 ml of saturated hydrogen chloride methanol solution was added dropwise with stirring at room temperature, and the mixture was stirred at room temperature for 1 hour. went. After completion of the reaction, the solvent was evaporated, ethyl acetate was added, and the mixture was neutralized with aqueous sodium hydrogen carbonate. The ethyl acetate layer was separated, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate) to give 0.38 g.
I got the object. The target compound shows a paste-like (nD 1.5410 21 ° C.) physical property immediately after isolation, but can be isolated as a crystal when left standing. Physical properties: melting point 153.1 ° C., yield 93.5%.

The agricultural and horticultural insecticide containing the hydrazine derivative represented by the general formula (I) of the present invention as an active ingredient is paddy rice, vegetables,
Suitable for various agricultural and forestry that damages fruit trees, other crops, flowers, etc., horticulture, pest control such as stored-grain pests, sanitary pests, nematodes, etc.
orana fasciata), Chanocokamon Aster (Ado-xo)
phyes sp.), apple coco inui (Grapholita inopina)
ta), Japanese pear squid (Grapholita mlesta), bean squid (Leguminivora glycinivorella), squirrel (Olethreutes mori), Chanohosuga (Caloptil)
ia thevivora), apple worm (Caloptilia zachrysa)
), Kingmon Hosoga (Phyllonorycterringoniella)
), Nashihosuga (Spulerinaastaurota), Pieris rapae crucivora (Pie-rs rapae crucivora), Helicoverpa armigera (Heliothis sp.), Codling moth (L-aspeyresia pomon)
ella), diamondback moth (Plutella xylostella), apple apple turtle (Argyresthia conjugella), peach mosquito (Carposina niponensis), lizard (Chilo suppre)
ssalis), Cobb Nomeiga (Cnaphalocrocis medinali)
s), Chamadara moth (Ephestia elutella), Kwanoma moth (Glyphodes pyloa-lis), Sanka moiga (Sc)
irpophaga incertulas), Ichimonjisiseseri (Parna-ra
guttata), armyworm (Pseudaletia separata), rice armyworm (Sesamia i-nferens), common earworm (Sp)
odoptera litura), Spodoptera litura (Spodopte)
ra exigua) and other lepidopterous insects, Leafhopper leafhopper (Macr
osteles fasci-frons), Green leafhopper (Nephotet)
tixcincticeps), brown planthopper (N-ilaparvata luge
ns), white-bellied planthopper (Sogatella furcifera), citrus whitefly (Diaphorina citri), whitefly white (Al)
eurolobus taonabae), tobacco whitefly (Bemisia ta)
baci), whitefly (Trialeurodes vaporari-
orum), Aphids (Lipaphis erysim)
i), green peach aphid (Myzus persicae), black weevil (Ceroplastes ceriferus), citrus scale insect (Pulvinaria aurantii), mandarin insect scale insect (Pseudaonidiaduplex), nashi marine scale insect (Comstockaspis perniciosa), and unasperus serrata (Unaspica). Pests of the order Lepidoptera, Pleurotus lenchus (Praty-lenchus sp.), Anemonal
a rufocuprea), Japanese beetle (Popilliajaponica),
Tobacco beetle (Lasioderma serricorne), flat beetle (Lyctus brunneus), pearl weevil (Epilachna vigintioctopu-nctata), weevil weevil (Callosobruchus chinensis), weevil (L-istroderus cossius, costirostris)
philus zeamais), boll weevil (Anthonomus grand)
is grandis), rice weevil (Lissorhoptrus o-ry)
zophilus), corn rootworm (Aulacophora femoralis),
O-ulema oryzae, Phyllotreta striolata, Weevil (Sitoph)
ilus zeamais), pine beetle (Tomicus piniper)
da), Colorado potato bite (Leptinotarsa decemli
neata), Mexican bean bottle (Epilachna vari)
vestis), cone-towers (Diabrotica sp.),
Coleoptera pests, such as the fruit fly (Dacus (Zeugodacus) cucu
rbitae), orange fruit fly (Dac-us (Bactrocera) dorsa
lis), rice leaf fly (Agromyza oryzae), onion fly (Delia antiqua), sand fly (Delia platur)
a), soybean fly, Asphondylia sp., housefly, Musca domestica, Culex p-ipie
ns pipiens) and other dipteran pests, Pratylenchu-s coffeae, Potato cyst nematode (Globodera rostochiensis), Nematode nematode (Meloidogyne sp.), Citrus nematode (Tyle)
nchulus sem-ipenetrans), Astragalus medicinalis (Aphelenchus avenae), Agarensis (Aphelenc)
It also has an insecticidal effect against the nematodes such as Hoides ritzemabosi), and particularly against pests such as Lepidoptera and Coleoptera. The scientific names are based on the Agriculture, Forestry Pests and Insects Directory 1987 edition (edited by the Japan Society of Applied Entomology and Entomology).

The agricultural and horticultural insecticide of the present invention has a remarkable insecticidal effect against the above-mentioned pests or sanitary pests which harm paddy fields, fruit trees, vegetables, other crops, flowers and the like. According to the expected time of occurrence, before or when the occurrence of pests is confirmed, paddy fields, fruit trees, vegetables, other crops, paddy water such as flowers, foliage or soil, etc. The insecticide of the present invention exerts the intended effect by treating the inside of a house, a groove in the vicinity of a house, or the like where the above-mentioned harmful insects that cause harmful effects on the above are predicted to occur. However, the present invention is not limited to only these aspects.

When the hydrazine derivative represented by the general formula (I) of the present invention is used as an agricultural and horticultural insecticide, it should be prepared in a convenient shape according to a conventional method for pesticide formulation. It is common. That is, the hydrazine derivative represented by the general formula (I) of the present invention is dissolved, separated, or suspended by mixing these in an appropriate inert carrier or, if necessary, an auxiliary agent in an appropriate ratio. It may be turbid, mixed, impregnated, adsorbed or attached, and then used by formulating into an appropriate dosage form such as a suspension, emulsion, liquid, wettable powder, granule, powder or tablet. The inert carrier which can be used in the present invention may be either solid or liquid, and examples of the material which can be a solid carrier include soybean flour, cereal flour, wood flour, bark flour, sawdust powder and tobacco stem flour. , Walnut shell powder, bran, fibrous powder, residue after extraction of plant extract, synthetic polymer such as ground synthetic resin, clays (eg kaolin, bentonite, acid clay etc.), talc (eg talc, pyrophyllide etc.), Silicas (for example, diatomaceous earth, silica sand, mica, white carbon [hydrous fine powder silicon, synthetic highly dispersed silicic acid also called hydrous silicic acid, some of which include calcium silicate as a main component depending on the product]), activated carbon, sulfur powder, Pumice stone, calcined diatomaceous earth, crushed bricks, fly ash, sand, calcium carbonate, inorganic mineral powder such as calcium phosphate, ammonium sulfate, ammonium phosphate, ammonium nitrate,
Chemical fertilizers such as urea and ammonium chloride, compost, etc.
These are used alone or in the form of a mixture of two or more kinds.

The material which can be used as a liquid carrier is selected from those having solvent ability per se, and those having no solvent ability but capable of dispersing the active ingredient compound with the aid of an auxiliary agent. The following carriers can be mentioned as typical examples, and these can be used alone or in the form of a mixture of two or more kinds, and for example, water, alcohols (for example, methanol, ethanol, isopropanol, butanol). -, Ethylene glycol, etc.), 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, diocluphthalate, etc.), amides (eg dimethylformamide, diethylformamide, dimethylacetamide) Etc.), nitriles (for example, acetonitrile, etc.), dimethyl sulfoxides, and the like. As the other auxiliary agents, the representative auxiliary agents exemplified below can be mentioned. These auxiliary agents are used according to the purpose, and are used alone or, in some cases, in combination of two or more kinds of auxiliary agents, or In some cases it is possible to use no adjuvant at all.

Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compound, for example polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxy. Ethylene higher fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkyl aryl sulfonate, naphthalene sulfonic acid condensate,
Examples thereof include surfactants such as lignin sulfonate and higher alcohol sulfate.

For the purpose of stabilizing the dispersion of active ingredient compounds, adhering and / or binding, the following auxiliary agents can be used, for example, casein, gelatin, starch,
It is also possible to use auxiliary agents such as methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, pine oil, bran oil, bentonite and lignin sulfonate. The following auxiliaries can also be used for improving the flowability of the solid product, for example waxes, stearates, alkyl phosphates and the like. As a deflocculant for a suspending product, an auxiliary agent such as a naphthalenesulfonic acid condensate or a condensed phosphate can be used. As the defoaming agent, for example, an auxiliary agent such as silicone oil may 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, or 0. 0 in the case of emulsion or wettable powder. 01 to 50% by weight is suitable. The agricultural and horticultural insecticide containing the hydrazine derivative represented by the general formula (I) of the present invention as an active ingredient is used as it is or in a form diluted or suspended appropriately with water or the like in order to control various harmful insects. Then, an effective amount for controlling pests may be applied to the pests, or applied to a place where the generation or growth of the pests is not preferable.

The amount of the agricultural and horticultural insecticide containing the hydrazine derivative represented by the general formula (I) of the present invention as an active ingredient depends on various factors such as the purpose, the target pest, the growing condition of the crop, and the tendency of the pest to grow. Although it may vary depending on the weather, environmental conditions, dosage form, application method, application site, application time, etc., it may be appropriately selected from the range of 0.1 g to 5 kg per 10 aal as the active ingredient compound according to the purpose. Agricultural and horticultural insecticides containing the hydrazine derivative represented by the general formula (I) of the present invention as an active ingredient, further pests to be controlled, for the purpose of expanding a suitable period for control, or for the purpose of reducing the dosage of other insecticides. Alternatively, it can be used by mixing with a bactericide.

Typical formulation examples and test examples of the present invention are shown below, but the present invention is not limited thereto.
In the prescription examples, “part” means “part by weight”.

Prescription example 1   50 parts of the compound of the present invention   Xylene 40 parts   Polyoxyethylene nonylphenyl ether and ether   Mixture with calcium rukylbenzene sulfonate 10 parts The above is uniformly mixed and dissolved to obtain an emulsion.

Prescription example 2   Inventive compound 3 parts   Cray powder 82 parts   Diatomaceous earth powder 15 parts The above is uniformly mixed and pulverized to obtain a powder.

Formulation Example 3 Compound of the present invention 5 parts Mixed powder of bentonite and clay 90 parts 5 parts of lignin sulfonate calcium 5 parts or more are uniformly mixed, and an appropriate amount of water is added and kneaded to granulate,
Dry to make granules.

Prescription example 4   20 parts of the compound of the present invention   Kaolin and synthetic highly dispersed silicic acid 75 parts   Polyoxyethylene nonylphenyl ether and al   Mixture with calcium benzene sulfonate 5 parts The above is uniformly mixed and pulverized to obtain a wettable powder.

Test Example 1: Spodoptera
Insecticidal test against litura) Cabbage leaf pieces (variety: four seasons harvest) were 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 500 ppm. After air-drying, it was placed in a plastic dish having a diameter of 9 cm, inoculated with the second-instar larva of Spodoptera litura, then covered and allowed to stand in a thermostatic chamber at 25 ° C. Eight days after the inoculation, the number of live and dead insects was investigated, the mortality rate was calculated by the following formula (Equation 1), and the determination was made according to the following criteria. 1 ward 10 heads 3 stations

[Equation 1] Criteria. A: 100% mortality rate B: 99% to 90% mortality rate C: 89% to 80% mortality rate D: 79% to 50% mortality rate Show.

[0034]

[Table 3]

Test Example 2: Kokuzo (Sitophilus)
Zeamais) Insecticidal test for adult brown rice was soaked 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 200 ppm. Diameter 4 after air drying
It was placed in a glass dish of cm and inoculated with an adult elephant elephant, then covered and allowed to stand in a thermostatic chamber at 25 ° C. The number of live and dead insects was examined 8 days after the inoculation, the mortality rate was calculated according to Test Example 1, and the determination was made according to the criteria of Test Example 1. 1 ward 10 heads 3 consecutive system. The results are shown in Table 4.

[0036]

[Table 4]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C07C 255/60 8519-4H 309/65 9160-4H 317/32 7419-4H 317/34 7419-4H 323/32 7419-4H 323/48 7419-4H

Claims (14)

[Claims] 1. A compound represented by the general formula (I): (In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different,
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 alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group or a lower alkylsulfonyl group And Y may be the same or different, and is a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group. , A lower haloalkylthio group, a lower haloalkylsulfinyl group, a lower haloalkylsulfonyl group, a lower alkynyl group or a lower alkoxycarbonyl group, Z may be the same or different, and a halogen atom, a nitro group, a cyano group, a lower alkyl group, a lower alkyl group, Halo Archi Group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkylsulfinyl group, lower haloalkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylsulfonyl group, lower haloalkylsulfonyloxy group, lower alkylcarbonyl group Or a phenoxy group, and 1, m and n each represent an integer of 0 to 5). 2. In the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different, represent a hydrogen atom or a lower alkyl group, X may be the same or different, and are halogen. An atom, a lower alkyl group, or a lower haloalkyl group, Y may be the same or different, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower haloalkylthio group or a lower haloalkylsulfinyl group, and Z is They may be the same or different and represent 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, and l, m and n
Are each an integer of 0 to 3. The hydrazine derivative according to claim 1. 3. In the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different, represent a hydrogen atom or a lower alkyl group, X may be the same or different, and are halogen. Atom, a lower alkyl group or a lower haloalkyl group, Y may be the same or different, a cyano group, a nitro group or a lower haloalkylsulfinyl group, Z may be the same or different, a halogen atom, a lower haloalkyl group or The hydrazine derivative according to claim 2, which represents a lower haloalkoxy group, and l, m and n each represent an integer of 1 to 3. 4. In the general formula (I), at least one X is 3
4. The hydrazine derivative according to claim 3, wherein the hydrazine derivative is substituted at position 4, at least one Y is substituted at position 4, and at least one Z is substituted at position 4. 5. A compound represented by the general formula (II): (In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different,
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 alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group or a lower alkylsulfonyl group And Y may be the same or different, and is a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group. , A lower haloalkylthio group, a lower haloalkylsulfinyl group, a lower haloalkylsulfonyl group, a lower alkynyl group or a lower alkoxycarbonyl group, Z may be the same or different, and a halogen atom, a nitro group, a cyano group, a lower alkyl group, a lower alkyl group, Halo Archi Group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkylsulfinyl group, lower haloalkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylsulfonyl group, lower haloalkylsulfonyloxy group, lower alkylcarbonyl group Or a phenoxy group, and l, m and n each represent an integer of 0 to 5), and a hydrazone represented by the general formula (I) (In the formula, R ¹ , R ² , R ³ , R ⁴ , X, Y, Z, l, m and n are the same as the above.). 6. A compound represented by the general formula (I): (In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different,
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 alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group or a lower alkylsulfonyl group And Y may be the same or different, and is a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group. , A lower haloalkylthio group, a lower haloalkylsulfinyl group, a lower haloalkylsulfonyl group, a lower alkynyl group or a lower alkoxycarbonyl group, Z may be the same or different, and a halogen atom, a nitro group, a cyano group, a lower alkyl group, a lower alkyl group, Halo Archi Group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkylsulfinyl group, lower haloalkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylsulfonyl group, lower haloalkylsulfonyloxy group, lower alkylcarbonyl group Alternatively, an agricultural and horticultural insecticide, which comprises a hydrazine derivative represented by a phenoxy group, wherein l, m and n each represent an integer of 0 to 5) as an active ingredient. 7. In the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different, represent a hydrogen atom or a lower alkyl group, X may be the same or different, and are halogen. An atom, a lower alkyl group, or a lower haloalkyl group, Y may be the same or different, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower haloalkylthio group or a lower haloalkylsulfinyl group, and Z is They may be the same or different and represent 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, and l, m and n
The insecticides for agricultural and horticultural use according to claim 6, wherein each represents an integer of 0 to 3. 8. In the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different, represent a hydrogen atom or a lower alkyl group, X may be the same or different, and are halogen. Atom, a lower alkyl group or a lower haloalkyl group, Y may be the same or different, a cyano group, a nitro group or a lower haloalkylsulfinyl group, Z may be the same or different, a halogen atom, a lower haloalkyl group or The insecticide for agricultural and horticultural use according to claim 7, which represents a lower haloalkoxy group, and l, m and n each represent an integer of 1 to 3. 9. In the general formula (I), at least one X is 3
The insecticide for agricultural and horticultural use according to claim 8, wherein at least one Y is substituted at the 4-position, and at least one Z is substituted at the 4-position. 10. A general formula (I) for controlling useful crops from pests: (In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different,
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 alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group or a lower alkylsulfonyl group And Y may be the same or different, and is a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group. , A lower haloalkylthio group, a lower haloalkylsulfinyl group, a lower haloalkylsulfonyl group, a lower alkynyl group or a lower alkoxycarbonyl group, Z may be the same or different, and a halogen atom, a nitro group, a cyano group, a lower alkyl group, a lower alkyl group, Halo Archi Group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkylsulfinyl group, lower haloalkylsulfinyl group, lower alkylsulfonyl group, lower haloalkylsulfonyl group, lower haloalkylsulfonyloxy group, lower alkylcarbonyl group Or a phenoxy group, and l, m and n each represent an integer of 0 to 5), and an agricultural and horticultural insecticide containing an hydrazine derivative represented by the following formula as an active ingredient in an amount of 10 a. A method for controlling pests, which comprises applying 1 g to 5 kg per pack. 11. In the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different, represent a hydrogen atom or a lower alkyl group, X may be the same or different, and are halogen. An atom, a lower alkyl group, or a lower haloalkyl group, Y may be the same or different, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower haloalkylthio group or a lower haloalkylsulfinyl group, and Z is They may be the same or different and represent 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, and l, m and n
Each represent an integer of 0 to 3).
Control method described. 12. In the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different, represent a hydrogen atom or a lower alkyl group, X may be the same or different, and are halogen. Atom, a lower alkyl group or a lower haloalkyl group, Y may be the same or different, a cyano group, a nitro group or a lower haloalkylsulfinyl group, Z may be the same or different, a halogen atom, a lower haloalkyl group or Represents a lower haloalkoxy group, wherein l, m and n are each 1 to 3
The method of controlling a pest according to claim 11, wherein 13. The control according to claim 12, wherein 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. Method. 14. The control method according to claim 13, wherein the pest is a Lepidoptera pest or a Coleoptera pest.