JP2879175B2 - Hydrazine derivatives and their production, use and use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound of the formula (I)

Embedded image (Wherein 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, and represents 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 a halogen atom, cyano group, nitro group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower alkylsulfinyl group, 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 Haloalk 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);
It is related to uses and usage.

[0002]

BACKGROUND OF THE INVENTION Insecticides and pesticides comprising hydrazine derivatives are disclosed, for example, in JP-A-48-91223 and JP-A-48-123223.
No. 122261, No. 56-45452 and No. 63-
No. 93761.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to provide a more useful insecticide.
The present invention has been accomplished by finding that the hydrazine derivative represented by the general formula (I) is a novel compound not 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 mentioned.

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

[0005] The present reduction reaction can be carried out by catalytic reduction in the presence of a suitable reducing agent or a catalyst. In a 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 to be used may be selected from the range of equimolar to excess molar in terms of the number of moles of hydride of the reducing agent with respect to the hydrazone represented by the general formula (II).

The inert solvent which can be used in this reaction includes:
Any material that does not significantly inhibit the progress of this reaction may be used, for example, methanol, ethanol, propanol, butanol.
Alcohols such as ethyl ether, chain ethers such as diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran, cellosolves such as methyl cellosolve, esters such as ethyl acetate, benzene, toluene, Aromatic hydrocarbons such as xylene, dichloromethane, chloroform, halogenated hydrocarbons such as carbon tetrachloride, diglyme,
Examples thereof include dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, water, and the like. These inert solvents may be used alone or in combination.

The reaction is carried out under acidic or neutral conditions at pH 1-7.
And preferably in the range of pH 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 is not fixed depending on the reaction scale, the reaction temperature and the like, but is in the range of several minutes to 48 hours. After completion of the reaction, the target product can be produced from the reaction solution containing the target product by a conventional method, for example, solvent distillation, solvent extraction, etc., and if necessary, purification by recrystallization, column chromatography, or the like. it can.

Next, when performing catalytic reduction as a reduction reaction,
For example, the reaction may be carried out in accordance with a conventional method described in "Shin Jikken Kagaku Koza" (Vol. 15-II: Maruzen). For example, usable inert solvents include, for example, methanol, ethanol, propanol and butanol. Alcohols such as methyl, cellosolves such as methyl cellosolve, cyclic ethers such as dioxane and tetrahydrofuran, hydrocarbons such as hexane and cyclohexane, acetic acid, fatty acids such as acetic acid ethyl ester and the like, N, N-dimethylformamide, 1,3
Examples thereof include amides such as -dimethyl-2-imidazolidinone and N-methylpyrrolidone, and these inert solvents may be used alone or as a mixture.

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

[0010] 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 preferably from room temperature to 80 ° C. The reaction time is not constant depending on the reaction scale, the reaction temperature and the like, but is in the range of several minutes to 80 hours. After completion of the reaction, the target substance can be produced by treating the reaction solution containing the target substance in the same manner as when a reducing agent is used.

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

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , X, Y, Z, 1, m and n are the same as 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 compound represented by the general formula (II)
The aniline represented by the formula (I) is reacted in the presence of an inert solvent, in the presence or absence of a base and / or a condensing agent, or a compound represented by the general formula (VI) and a compound represented by the general formula (V) The hydrazone derivative represented by the general formula (II) can be produced by reacting a halide represented by the formula (1) with an inert solvent and a base.

The compounds represented by the general formula (IV) are described in JP-A-62-223169 and JP-A-6-70462,
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-
2667 (1960).

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

Embedded image

[Table 1] Table 2 shows the NMR data of the paste-like material in Table 1.

[Table 2]

[0015]

The present invention will be described in more detail with reference to the following Examples, which by no means limit the present invention.

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

Embedded image 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: melting point 220 ° C, yield 60.2%.

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

Embedded image 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: melting point 164-165 ° C, yield 65.0
%.

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

Embedded image 2- [N- (4-cyanobenzyl)-obtained in 1-2
N- (3-trifluoromethylphenyl)] hydrazono 0.20 g (0.4 mmol) of 4-chloroacetanilide is 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), 0.7 ml of a saturated hydrogen chloride methanol solution was added dropwise with stirring at room temperature, and the mixture was stirred 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 bicarbonate. 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)

Embedded image 0.40 g (0.8 mmol) of 2- [N- (4-cyanobenzyl) -N- (3-trifluoromethylphenyl)] hydrazono 4-trifluoromethoxyacetanilide was added to 3 ml of tetrahydrofuran and 7 ml of methanol. The mixture was dissolved in a mixed solvent, 0.05 g (0.8 mmol) of sodium cyanoborohydride was added, and 0.5 ml of a saturated methanol solution of hydrogen chloride was added dropwise with stirring at room temperature, followed by stirring at room temperature for 1 hour. went. After completion of the reaction, the solvent was distilled off, ethyl acetate was added, the mixture was neutralized with aqueous sodium bicarbonate, 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.
Was obtained. The target compound exhibits paste-like properties (nD 1.5410 at 21 ° C.) immediately after isolation, but can be isolated as crystals when left to stand. Physical properties: melting point 153.1 ° C., yield 93.5%.

The agricultural and horticultural insecticides containing the hydrazine derivative represented by the general formula (I) of the present invention as an active ingredient are 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-brushed moth (Spulerinaastaurota), cabbage 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)
tixcincticeps), brown planthopper (N-ilaparvata luge)
ns), Shirako groundhopper (Sogatella furcifera), citrus lice (Diaphorina citri), grape whitefly (Al)
eurolobus taonabae, tobacco whitefly (Bemisia ta)
baci), Whiteflies (Trialeurodes vaporari-
orum) and the radish aphid (Lipaphis erysim)
i), peach aphid (Myzus persicae), horned beetle (Ceroplastes ceriferus), citrus stag beetle (Pulvinaria aurantii), citrus stalk beetle (Pseudaonidiaduplex), pear stag beetle (Comstockaspis perniciosa), etc. Pterodactyl pests, Praty-lenchus sp.
a rufocuprea), Bean beetle (Popilliajaponica),
Tobacco beetle (Lasioderma serricorne), Flying bark beetle (Lyctus brunneus), Japanese beetle (Epilachna vigintioctopu-nctata), Adzuki beetle (Callosobruchus chinensis), Larch beetle (L-istroderes costirostris)
philus zeamais), a weevil (Anthonomus grand)
is grandis), rice water weevil (Lissorhoptrus o-ry)
zophilus), cricket beetle (Aulacophora femoralis),
Insect beetle (O-ulema oryzae), beetle flea beetle (Phyllotreta striolata), weevil (Sitoph)
ilus zeamais), pine bark beetle (Tomicus piniper)
da), Colorado potato beetle (Leptinotarsa decemli)
neata), Mexican beans (Epilachna vari)
vestis), corn worms (Diabrotica sp.),
Coleopteran pests, such as sea flies (Dacus (Zeugodacus) cucu
rbitae), Citrus fruit fly (Dac-us (Bactrocera) dorsa
lis), rice leaf fly (Agromyza oryzae), onion fly (Delia antiqua), and fly (Delia platur)
a), soybean flies (Asphondylia sp.), houseflies (Musca domestica), and mosquitoes (Culex p-ipie)
ns pipiens), Pterylenchu-s coffeae, potato cyst nematodes (Globodera rostochiensis), root-knot nematodes (Meloidogyne sp.), tangerine nematodes (Tyle)
nchulus sem-ipenetrans), Nenegrass nematode (Aphelenchus avenae), Hagare nematode (Aphelenc)
It also has an insecticidal effect against pest insects such as honeysuckles (Hoides ritzemabosi), and particularly has a remarkable effect on pests such as lepidoptera and beetle. 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 hydrazine derivative represented by the general formula (I) of the present invention is used as a pesticide for agricultural and horticultural use, it is preferable to formulate it into a convenient form according to a conventional method for pesticide formulation. General. That is, the hydrazine derivatives represented by the general formula (I) of the present invention are dissolved, separated and suspended by mixing them in a suitable inert carrier or, if necessary, together with an auxiliary in a suitable 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 bricks, fly ash, sand, calcium carbonate, calcium phosphate, ammonium sulfate, phosphorous ammonium, ammonium nitrate,
Urea, chemical fertilizers such as salt and salt, compost and the like,
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 adjuvant without having 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. 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, sticking and / or binding, the following auxiliaries can be used. For example, casein, gelatin, starch,
Auxiliaries such as methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, pine oil, bran oil, bentonite, and ligninsulfonate 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 as required. 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 hydrazine 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 hydrazine 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, and the tendency of the pest to occur. The active ingredient compound may be appropriately selected from the range of 0.1 g to 5 kg per 10 al according to the purpose, although it varies depending on the weather, environmental conditions, dosage form, application method, application place, application time and the like. Agricultural and horticultural insecticides containing the hydrazine derivative represented by the general formula (I) of the present invention as an active ingredient are further controlled as pests, other insecticides for the purpose of extending a suitable period of control, or for reducing the amount of drugs. Alternatively, it can be used in combination with a bactericide.

The following are typical formulation examples and test examples of the present invention, but the present invention is not limited to these.
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 5 parts of the compound of the present invention 90 parts of a mixed powder of bentonite and clay 5 parts of calcium ligninsulfonate 5 parts 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 And

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 equation (Equation 1), and the judgment was made according to the following criteria. 10 units in 1 ward, 3 consecutive

(Equation 1) Judgment criteria. A: mortality rate 100% B: mortality rate 99% to 90% C: mortality rate 89% to 80% D: mortality rate 79% to 50% The results are shown in Table 3. Show.

[0034]

[Table 3]

Test Example 2: Sitophilus
zeamais) 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. Table 4 shows the results.

[0036]

[Table 4]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 241/02 C07C 241/02 253/30 253/30 255/58 255/58 255/60 255/60 309/65 309/65 317/32 317/32 317/34 317/34 323/32 323/32 323/48 323/48 // A01N 25/04 101 A01N 25/04 101 (56) References JP-A-54-151925 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C07C 243/22 A01N 37/22 A01N 37/34 A01N 41/04 A01N 41/10 C07C 241/02 C07C 253/30 C07C 255/58 C07C 255/60 C07C 309/65 C07C 317/32 C07C 317/34 C07C 323/32 C07C 323/48 CA (STN) REGISTRY (STN)

Claims (14)

(57) [Claims] 1. A compound of the general formula (I) (Wherein 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, and represents 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 a halogen atom, cyano group, nitro group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower alkylsulfinyl group, 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 Haloalk 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). 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 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; 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; l, m and n
The hydrazine derivative according to claim 1, wherein each 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, represent a hydrogen atom or a lower alkyl group, X may be the same or different, and 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, wherein the hydrazine derivative 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
The hydrazine derivative according to claim 3, wherein at least one Y is substituted at the 4-position, and at least one Z is substituted at the 4-position. 5. A compound of the general formula (II) (Wherein 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, and represents 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 a halogen atom, cyano group, nitro group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower alkylsulfinyl group, 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 Haloalk 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), wherein the hydrazone represented by the general formula (I) is reduced with a reducing agent. (Wherein R ¹ , R ² , R ³ , R ⁴ , X, Y, Z, 1, m and n are the same as described above). 6. A compound of the general formula (I) (Wherein 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, and represents 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 a halogen atom, cyano group, nitro group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower alkylsulfinyl group, 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 Haloalk 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), 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 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; 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; l, m and n
7 represents an integer of 0 to 3, respectively. 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 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 agricultural and horticultural insecticide according to claim 7, wherein the insecticide for agricultural and horticultural use 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
9. The agricultural and horticultural insecticide 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. Formula (I) for controlling useful crops from pests (Wherein 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, and represents 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 a halogen atom, cyano group, nitro group, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower alkylsulfinyl group, 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 Haloalk 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). An agricultural and horticultural insecticide containing a hydrazine derivative represented by the formula A method for controlling pests, which is applied in an amount of 1 g to 5 kg per liter. 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 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; 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; l, m and n
Each represents an integer of 0 to 3).
The 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 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, and l, m and n each represent 1 to 3
The control method according to claim 11, which is represented by: 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 method according to claim 13, wherein the pest is a lepidopteran or a beetle.