JP2937415B2 - Pyridazinone derivative and insect pest control agent - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel 3 (2H) -pyridazinone derivative and a pesticide containing the derivative as an active ingredient.

[Conventional technology]

 The following patents relate to the present invention.

European Patent Publication 0088384 European Patent Publication 0134439 European Patent Publication 0183212 European Patent Publication 0199281 European Patent Publication 0210647 European Patent Publication 0193853 European Patent Publication 0232825 European Patent Publication 0302346 Known compounds contained in these patents Is represented by the following general formula (II).

The features of these patents are described, for example, in European Patent Publication 00.
In 88384, EP-A-0134439, EP-A-0183212, EP-A-0199281 and EP-A-0232825, Y 'is an oxygen atom or a sulfur atom, but A' is a substituent such as halogen. And European Patent Publication 0210647.
In the symbol, R 'is an aryl group,
European Patent Publication 0302346 is characterized in that R 'is a substituent such as an alkyl group substituted by a halogen atom. European Patent Publication No. 0193853 is characterized in that Y 'is a nitrogen atom or an oxygen atom, but A' is a substituent such as halogen. The compound of the present invention is a novel compound not included in these prior arts.

(Aspect of the invention)

The present invention relates to a compound of the general formula [I]: [Wherein, R represents an alkyl group having 1 to 4 carbon atoms substituted by a cycloalkyl group having 3 to 8 carbon atoms, an alkyl group having 1 to 4 carbon atoms substituted by a phenyl group which may be substituted, R ¹ represents a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms or a hydroxy group, which is substituted by a heterocyclic group which may be substituted; Or a haloalkyl group having 1 to 3 carbon atoms, provided that
R ² , Rc, Rd and Re each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Rf represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, Represents a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group which may be substituted or a heterocyclic group which may be substituted, X is -O-, -S-, -NH- or (Rg represents an alkyl group having 1 to 4 carbon atoms);
l represents a halogen atom, and Q represents an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted heterocyclic group. ｝ Represent. The present invention relates to a 3 (2H) -pyridazinone derivative represented by the formula: and a pesticidal agent containing one or more of such derivatives as an active ingredient. The present inventors have found that the compound of the present invention represented by the general formula [I] has an excellent pest control effect.

For example, known compounds represented by the general formula [II] include strong insecticides, mites, nematicides. Although it has a bactericidal activity, a broad insecticidal spectrum and excellent fast-acting properties, the compound of the present invention has an effect of inhibiting the transformation of pests and is therefore slow-acting.

Also, the compounds of the present invention are effective against various harmful pests at extremely low drug concentrations.

The pests include, for example, agricultural pests such as the black leafhopper, brown planthopper, brown peach aphid, diamondback moth, lotus serrata, spider mite, orange mites, kanzawa spider mite, etc. House dust pests, such as termites of house pests, livestock pests such as mites, fleas, lice, flies, etc., indoor dust mites such as acarid mites, Dermatophagoides, clawed mites, slugs of mollusks, snails and the like. .

That is, they found that they could be effectively controlled against Orthoptera, Termites, Hemiptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera and mites and lice.

This effect was specifically described in the biological test example described later.

In J of the above general formula (I), when Q represents an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted cycloalkyl group,
Examples of the type of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkyloxy group, an alkenyloxy group, an alkynyloxy group, a methylenedioxy group, a halogenomethylenedioxy group, and an alkylthio group. , Alkenylthio, alkylsulfenyl, alkylsulfonyl, cycloalkyloxy, haloalkyl, haloalkyloxy, haloalkylthio, alkylamino, alkylcarbonylamino, nitro, cyano, hydroxyl, alkylcarbonyl Group, alkoxycarbonyl group, carboxyl group, aryl group, aryloxy group, arylthio group, arylamino group, arylcarbonyl group, arylmethyleneoxy group, aryloxymethyl group, arylmethylenecarbo Group, unsubstituted or substituted pyridyloxy group, hydroxyalkyl group, alkylcarbonyloxyalkynyl group, alkoxyalkyl group, alkylthioalkyl group, alkylcarbonylalkyl group, alkoxycarbonylalkyl group, cyanoalkyl group, haloalkylcarbonyl group And the like.

In the above formula (I), when Q is a heterocyclic group, examples of the heterocyclic ring include thiophene, furan, pyrrole, imidazole, thiazole, oxazole, pyrazole, pyridine, pyridazine, pyrimidine, virazine and benzoxazole. , Benzthiazole, benzothiophene, dibenzothiophene, benzofuran, benzimidazole, indole, indazole, quinoline,
Isoquinoline, quinoxaline, tetrahydrothiophene, tetrahydrothiopyran, oxirane, tetrahydrofuran, tetrahydropyran, pyrrolidine, piperidine, morpholine, thiomorpholine, piperazine, isoxazole, oxadiazole, thiadiazole, imidazoline, imidazolone, imidazolidone, hydantoin, oxazoline, oxazoline Uracil, triazolone and the like.

In the case of a heterocyclic group having a substituent, examples of the type of the substituent include a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, a haloalkyl group, a haloalkoxy group, a nitro group, a cyano group,
Examples include an alkylcarbonyl group, a phenyl group, and a substituted aryl group.

The compounds of the present invention can be prepared by a number of methods. These methods are, for example, as follows.

[In the schemes (1), (2) and (3),
R, R ¹ , X, Rc, Rd, Re, Rf, Q and J have the same meanings as described above, Z ¹ represents a halogen atom or an azole group, and Z ² represents a halogen atom, an alkylsulfonate group and an arylsulfonate group. Wherein Z ³ represents a halogen atom, and R ⁴ represents a substituent having a reactive functional group. In the reactions represented by the schemes (1), (2) and (3), as the solvent, lower alcohols (eg, methanol, ethanol, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), hydrocarbons ( For example,
Benzene, toluene, etc.), ethers (eg, isopropyl ether, tetrahydrofuran, 1,4-dioxane, etc.), amides (eg, N, N-dimethylformamide, hexamethylphosphoric triamide, etc.), halogenated hydrocarbons (eg, For example, dichloromethane, dichloroethane, etc.) can be used. If necessary, a mixed solvent of these solvents or a mixed solvent with water can also be used. Examples of the base include inorganic bases (eg, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.) and organic bases (eg, sodium methoxide, sodium ethoxide, triethylamine, pyridine, etc.) ) Can be used. If necessary, a tetraammonium salt (for example, triethylbenzylammonium chloride or the like) may be added to the reaction system as a catalyst.
The reaction temperature can range from −20 ° C. to the boiling point of the solvent used in the reaction, but more preferably from −5 ° C. to the boiling point of the solvent used in the reaction. Although the molar ratio of the raw materials can be set arbitrarily, it is advantageous to carry out the reaction in an equimolar ratio or a ratio close thereto.

More specifically, the (1-a method) in the scheme (1) is a method in which Z ^{1 of the} compound represented by the general formula [III] and an alcohol represented by the general formula [IV] are appropriately reacted in the presence of a base. The compound [I] of the present invention can be produced by reacting in a solvent. Z ¹
Is preferably a halogen atom, especially a chlorine atom or a bromine atom,
Azoles, especially 1-imidazole groups, are preferred. As the solvent, N, N-dimethylformamide, methanol, ethanol, toluene and a mixed solvent of toluene and water are preferable, and as the base, an inorganic base is preferable, and particularly, sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide are preferable. The reaction temperature is preferably from 20 ° C to 50 ° C.

The (1-b method) in the scheme (1) is a method in which a pyridazinone derivative represented by the general formula [V] is converted into an alkyl halide or an alkyl sulfonate represented by the general formula [VI] in an appropriate solvent in the presence of a base. To produce the compound of the present invention. Z ² is preferably a chlorine atom or a bromine atom, and the solvent is preferably a mixed solvent of N, N-dimethylformamide, methanol, ethanol, acetonitrile, 1,2-dichloroethane, toluene, and toluene-water, and the base is an inorganic base. And particularly preferred are sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide. The reaction temperature is preferably from 20C to 120C. Sodium iodide, potassium iodide,
By adding tetrabutylammonium iodide or the like, the reaction can be accelerated and accelerated, and good results may be obtained.

In the method (2-a) of the scheme (2), the compound [I] of the present invention can be produced by alkylating the ² -position of the pyridazinone derivative [VII] with R-Z2 [VIII]. The addition of an inorganic base or an organic base to the reaction system enhances the reactivity of the pyridazinone derivative [VII], and facilitates the production of the compound of the present invention.

The (2-b method) in the scheme (2) is performed by chemically modifying the functional group in the N-substituent (R ⁴ ) of the pyridazinone derivative represented by the general formula [XI]. R) to produce the compound [I] of the present invention.

Specifically, a reduction method for dehalogenating a halogen atom contained in R ⁴ may be mentioned.

The (3-a method) in the scheme (3) is to react a compound represented by the general formula [III] with a compound represented by the general formula [XII] in a suitable solvent in the presence of a base. By
The compound of the present invention represented by the general formula [XIII] is produced. Further, this is a method for producing the compound of the present invention by reacting the compound with a heterocyclic halide or an acid halide represented by the general formula [XIV] in an appropriate solvent in the presence of a base.

As a solvent to be used, benzene, toluene, tetrahydrofuran, 1,2-dichloroethane, N, N-dimethylformamide and the like are preferable, and as a base, an organic base is preferable, and triethylamine, pyridine and the like are particularly preferable. In some cases, inorganic bases can also be used. Reaction temperature is 0
C. to 50 C. is preferred.

The scheme (3-b) in the scheme (3) is carried out by reacting a compound of the present invention represented by the general formula [XIII] with an isocyanate compound represented by the general formula [XV] in a suitable solvent. This is a method for producing an inventive compound.

As the solvent, benzene, toluene, tetrahydrofuran, 1,2-dichloroethane and the like are preferable, and the reaction temperature is preferably 0 ° C to 50 ° C.

If necessary, an organic base (eg, triethylamine, pyridine, hexamethylenetetramine, etc.) may be added to the reaction system.

The following reaction is also useful as a method for producing the compound of the present invention.

[In (Method 4-a) and (Method 4-d), R, _Rc and J have the same meaning. In the (Method 4-a), the compound of the present invention can be produced by dechlorination of the chloro group at the 4-position of the pyridazinone ring by a hydrogenation reaction. The application of this production method is limited to the case where the R group and the J group are stable against the hydrogenation reaction.

(Methods 4-b) and (4-c) are useful for synthesizing pyridazinone compounds containing a 2-aminoethyloxy group at the 5-position. The (4-b method) is characterized by passing through an acetal compound, and the (4-c method) is characterized by reducing a nitrile group.

(4-d method) is useful for synthesizing a pyridazinone compound containing a 2-hydroxyethyloxy group at the 5-position. It is characterized in that the corresponding 5-hydroxypyridazinone compound is heated in the presence of ethylene carbonate and a base.

Specific examples of the compounds included in the present invention include the compounds shown in Table 1 below. However, the compounds in Table 1 are for illustration only, and the present invention is not limited to these. In the table, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, Ph is an unsubstituted phenyl group, t is tertiary, s is secondary, and i is Indicates iso. In addition,
Compounds having an asymmetric carbon atom among the compounds included in the present invention include (+)-form and (-)-form of the optically active compound.

Further, among the compounds included in the present invention, when a configuration isomer is present, it includes cis- and trans-isomers.

Q1 to Q70 in the above Table 1 are groups represented by the following structural formula.

The following method for producing the compound of the present invention will be specifically described with reference to examples, but the compound of the present invention is not limited thereto.

Production Example 1 1.2 g of 2-benzyl-5-hydroxy-3 (2H) -pyridazinone, 1.3 g of 6-chloro-3-pyridinemethanol mesylate were dissolved in 20 ml of N, N-dimethylformamide,
1.1 g of anhydrous potassium carbonate was added, and the mixture was heated and stirred on an oil bath at 70 ° C. for 1 hour. After standing to cool, the precipitated solid was poured into water, and the precipitated solid was collected by filtration, washed with water, and recrystallized from acetonitrile to obtain the target compound (760 m).
g was obtained.

Melting point 161.7-162.5 ° C Production Example 2 2-benzyl-5-chloro-3 (2H) -pyridazinone
1.0 g and 0.64 g of 2- (2-pyridyloxy) -1-propanol are dissolved in 10 ml of N, N-dimethylformamide,
After adding 0.3 g of potassium hydroxide and stirring at room temperature for 24 hours, water was added, and the mixture was extracted with ethyl acetate. Wash the organic layer with water,
After drying over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure to obtain a brown oil. This was purified by column chromatography (silica gel, benzene / ethyl acetate = 3/1) to obtain 300 mg of the desired compound.

Melting point 75.3-75.9 ℃ Production Example 3 5- (2-aminoethyloxy) -2-benzyl-3
After dissolving 0.6 g of (2H) -pyridazinone (Compound No. 30 of the present invention) in 20 ml of benzene, 1 ml of triethylamine was added under ice-cooling.
And 0.3 g of ethyl chloroformate. The reaction mixture was stirred at room temperature for 2 hours, washed with a dilute aqueous hydrochloric acid solution, the benzene layer was washed with water, dried, and benzene was distilled off to obtain 0.7 g of crude crystals of the compound of the present invention. By recrystallization from isopropyl ether, white crystals of the compound of the present invention (0.5 g) were obtained.

73.5-78.0 ° C, melting point 4 A mixture of 1.3 g of 55% sodium hydride and 20 ml of N, N-dimethylformamide was cooled with ice, 5.7 g of N- (2-hydroxyethyl) -phthalimide was added, and 2-benzyl-5 was further added.
After adding 6.6 g of -chloro-3 (2H) -pyridazinone to the reaction solution, the mixture was allowed to stand at room temperature for 24 hours. When water is added to the reaction solution, crystals precipitate, and the crystals are separated by filtration, washed with water, dried and dried to give 2-benzyl-5- [2- (phthalimidoyl) ethyloxy]-.
7.9 g of 3 (2H) -pyridazinone was obtained. The obtained crude crystals were mixed with 50 ml of methylene chloride and 3.5 g of hydrazine hydrate, and heated and reacted at the reflux temperature for 4 hours. After cooling with air, the precipitated crystals were separated by filtration. After drying the methylene layer, the solvent is distilled off to obtain a crude crystal of the compound of the present invention.
3.8 g was obtained. Melting point 45-59 ° C Production Example 5 2-benzyl-5-chloro-3 (2H) pyridazinone 5
g, 5.2 g of sodium hydroxide, 18.7 g of 2-bromoethanol and 20 ml of water, a catalytic amount of tetrabutylammonium bromide was added, and the mixture was heated and reacted at reflux temperature for 9 hours. After cooling with air, the mixture was extracted with chloroform. The chloroform layer was washed with a dilute aqueous alkali solution, dried, and the solvent was distilled off to obtain 3.6 g of crude crystals of the compound of the present invention.

Production Example 6 2-benzyl-5-hydroxy-3 was added to 30 ml of N, N-dimethylformamide containing 0.43 g of 55% sodium hydride.
2 g of (2H) -pyridazinone was added, followed by 0.8 g of ethylene carbonate, and the mixture was heated at 120 ° C. for 3 hours. After cooling, water was added and extracted with ethyl acetate. After drying, the solvent was distilled off to obtain 0.6 g of crude crystals of the compound of the present invention.

Production Example 7 1.5 g of 2-benzyl-5-hydroxy-3 (2H) pyridazinone, 1.5 g of 2,4-dichlorobenzyl chloride, 1.2 g of anhydrous potassium carbonate and 30 m of N, N-dimethylformamide
l of the mixture was heated at 130 ° C. for 4 hours. After cooling, water was added, and the precipitated crystals were separated by filtration. The obtained crude crystals were washed with isopropyl ether and recrystallized from ethanol to give 1.9 g of the present compound as white crystals.

Melting point 138.2-140.2 ° C Production Example 8 5- (2-aminoethyloxy) -2-benzyl-3
A mixture of 0.9 g of (2H) -pyridazinone (Compound No. 30 of the present invention), 0.4 g of triethylamine, 0.4 g of cyclopropanecarboxylic acid chloride and 30 ml of methylene chloride was heated under reflux for 2 hours. After air cooling, the mixture was washed with a dilute aqueous hydrochloric acid solution, the methylene chloride layer was dried, and the solvent was distilled off to obtain crude crystals. Purification by silica gel column chromatography (distillate: benzene / ethyl acetate 1/1) yields 0.8 g of white crystals of the compound of the present invention.
I got

Melting point 159.6-161.2 ° C Production Example 9 1 g of 2-benzyl-5-hydroxy-3 (2H) -pyridazinone, 0.9 g of ethyl N- (2-chloroethyl) carbamate (ClCH ₂ CH ₂ NHCO ₂ C ₂ H ₅ ), 1.4 g of anhydrous potassium carbonate,
A catalytic amount of potassium iodide was added to a mixture of 30 ml of N, N-dimethylformamide and heated at 70-80 ° C for 7 hours. After the solvent was distilled off, water was added to the residue, and the mixture was extracted with chloroform.
After drying the chloroform layer, the crude crystals obtained by evaporation were washed with a mixed solvent of isopropyl ether / benzene to obtain 0.9 g of white crystals of the compound of the present invention.

Production Example 10 1 g of 2-benzyl-4-chloro-5- [2- (ethoxycarbonylamino) ethyloxy] -3 (2H) -pyridazinone (white crystals; melting point: 122.5 to 123.9 ° C) was added to ethanol.
Dissolve in 50 ml, add 5% palladium-carbon catalyst,
The mixture was vigorously stirred under an atmosphere of hydrogen fin to perform a dechlorination reaction at the 4-position. After the post-treatment, the reaction product was repeatedly purified by preparative thin-layer chromatography to obtain 0.1 g of white crystals of the compound of the present invention.

Production Example 11 1 g of the present compound No. 30 is dissolved in 10 ml of benzene, 0.4 g of ethyl isocyanate (CH ₂ H ₅ NCO) is added, and the mixture is stirred at room temperature to precipitate crystals. The crystals were separated by filtration and dried to obtain 0.9 g of white crystals of the compound of the present invention.

Melting point 169.0-171.5 ° C. Reference Example 1 Synthesis of 2-benzyl-5-hydroxy-3 (2H) -pyridazinone 2-benzyl-4,5-dichloro-3 (2H) -pyridazinone 60 g and potassium hydroxide 38.8 g in 250 ml of ethanol And 150 ml of water were added and heated to reflux temperature for 10 hours on an oil bath.
After the reaction, the solvent was distilled off under reduced pressure, 200 ml of water was added to the residue, and the mixture was washed twice with chloroform, and the aqueous layer was acidified with concentrated hydrochloric acid. The precipitated white solid was collected by filtration, washed with water, and dried to give 2-
55 g of benzyl-4-chloro-5-hydroxy-3 (2H) -pyridazinone were obtained. Next, 5.0 g of 2-benzyl-4-chloro-5-hydroxy-3 (2H) -pyridazinone was dissolved in an aqueous sodium hydroxide solution (1.82 g of NaOH, 20 ml of water),
200 mg of 5% Pd / C was added, and 474 ml of hydrogen gas was absorbed at normal pressure. After the reaction, Pd / C was removed by filtration, and the mixture was acidified by adding concentrated hydrochloric acid. The precipitated white solid was collected by filtration, washed with water and dried to give 2-
Benzyl-5-hydroxy-3 (2H) -pyridazinone 4.
1 g was obtained. Melting point 48-55 ° C Reference Example 2 5-Chloro-2- (cyclohexylmethyl) 3 (2H)-
Synthesis of pyridazinone 2- (cyclohexylmethyl) -5-hydroxy-3
To 10.5 g of (2H) -pyridazinone was added 25 ml of phosphorus oxychloride, and the mixture was heated at 85 ° C for 4 hours. After the reaction, excess phosphorus oxychloride was distilled off under reduced pressure. The residue was poured into water, made alkaline with an aqueous sodium hydroxide solution, and the precipitated solid was extracted with benzene. The benzene layer was washed with water, dried over anhydrous sodium sulfate, and filtered through silica gel. The benzene was distilled off under reduced pressure to obtain 6.4 g of the target compound. Melting point 81.6 ~
81.8 ° C. Reference Example 3 2-benzyl-5- (3-hydroxypropyloxy)
Synthesis of -3 (2H) -pyridazinone 2-benzyl-5-chloro-3 (2H) -pyridazinone
10g, 1,3-propanediol 50g, 85% potassium hydroxide
After reacting a mixture of 3.0 g and N, N-dimethylformamide at room temperature for 24 hours at room temperature, water was added to the reaction solution, followed by extraction with ethyl acetate.
4 g were obtained.

White crystals Melting point: 91-93 ° C. Table 2 shows the physical properties of the compounds produced according to any of the methods shown in Production Examples 1 to 11.

The compound numbers in Table 2 are referred to in the preparation examples and test examples described later.

The NMR data of Compound Nos. 14, 22, 30, 41 and 51 in Table 2 are as follows.

Compound No. 14 NMR (CDCl ₃ δ value): 1.19 (6H, t, J = 7 Hz), 3.58 (2H,
q, J = 7Hz), 3.62 (2H, q, J = 7Hz), 3.86 (2H, d, J = 5H)
z), 4.70 (1H, t, J = 5Hz), 5.14 (2H, s), 6.02 (1H,
d, J = 2.4Hz), 7.0-7.4 (5H, m), 7.60 (1H, d, J = 2.4H)
z). Compound No. 22 NMR (DMSO-d ₆ , δ value): 4.58 (2H, s), 5.27 (2H,
s), 6.15 (1H, m), 7.37 (5H, s), 7.70 (1H, m), 9.8
(1H, bs). Compound No. 30 NMR (CDCl ₃ , δ value): 1.45 (2H, bs), 3.05 (2H, t),
3.92 (2H, t), 5.25 (2H, s), 6.10 (1H, d), 7.35 (5
H, s), 7.60 (1H, d). Compound No. 41 NMR (CDCl ₃ , δ value): 3.5 (1H, bs), 4.00 (4 H, s),
5.30 (2H, s), 6.20 (1H, d), 7.40 (5H, s), 7.65 (1
H, d). Compound No. 51 NMR (CDCl ₃ , δ value): 1.20 (6H, t), 2.10 (2H, m),
3.4-3.8 (4H, m), 4.00 (2H, t), 4.66 (1H, t), 5.25
(2H, s), 6.14 (1H, d), 7.32 (5H, s), 7.55 (1H,
d). When the compound of the present invention is used as a pesticide, it is generally appropriate to use a suitable carrier, for example, a solid carrier such as clay, talc, bentonant, diatomaceous earth, water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons ( Benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), and acid amides (dimethylformamide, etc.). Add emulsifiers, dispersants, suspending agents, penetrants, spreading agents, stabilizers, etc., if necessary, and put them to practical use in any form such as emulsions, oils, wettable powders, powders, granules, flowables, etc. be able to. If necessary, it may be mixed with other kinds of herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like at the time of preparation or spraying. The applied amount of the compound of the present invention varies depending on the application scene, application time, application method, target pests, cultivated crops, and the like, but is generally 0.005 per hectare as an active ingredient.
About 50kg is appropriate.

Next, the mixing ratios and types of the various preparations of the present invention are described below.

The numerical values in the above table represent% by weight.

For use, emulsions, oils, floor buildings, wettable powders and granular wettable powders are diluted with a predetermined amount of water and sprayed, and powders and granules are directly sprayed without dilution with water. The granules also include a bait.

 Next, examples of each component in each of the above-mentioned preparations will be described.

Emulsion Active ingredient: Compound of the present invention Carrier: Xylene, dimethylformamide, methylnaphthalene, cyclohexanone, dichlorobenzene, isophorone Surfactant: Solpol 2680, Solpol 3005X Solpol 3353 Other ingredients: Piperonyl butoxide, Benzotriazole Oil agent Active ingredient: Compound of the present invention Carrier: Xylene, methylcellosolve, kerosene Flowable Active ingredient: Compound of the present invention Carrier: Water Surfactant: Lunox 1000C, Solpol 3353, Soprofl FL, Nippol, Agrisol S-710, Sodium ligninsulfonate Other components : Xanthan gum, formalin, ethylene glycol, propylene glycol wettable powder Active ingredient: Compound of the present invention Carrier: calcium carbonate, kaolinite, ziglite D, ziglite PFP, diatomaceous earth, talc Surfactant: Solpol 5039, Lunox 1000C, calcium lignin sulfonate, sodium dodecyl benzulfonate sodium 5050, solpol 005D, solpol 5029-0 Other components: Carplex # 80 Dust Active ingredient: Compound of the present invention Carrier: Carbonic acid Calcium, kaolinite, ziglite D, talc Other components: diisopropyl phosphate, carplex # 80 granule (1) Active ingredient: Compound of the present invention Carrier: calcium carbonate, kaolinite, bentonite, talc Other components: ligninsulfonic acid Calcium, polyvinyl alcohol Granule (2) [bait] Active ingredient: Compound of the present invention Carrier: Flour, bran, corn grit, siegrite D Other ingredients: Paraffin, soybean oil Granular wettable powder Active ingredient: The present invention Compound Carrier: Calcium acid, kaolinite, silylite, clay, ammonium sulfate, urea, white carbon Surfactant: Lunox 1000C, formalin condensate of naphthalene sulfonic acid, polyoxyethylene-nonyl phenyl ether, sodium lignin sulfonate Other components: epoxidation Stabilizers such as soybean oil and antioxidants Formulation examples of pest control agents containing the compound of the present invention as an active ingredient are shown below, but are not limited thereto. In the following formulation examples, "parts" means parts by weight.

Formulation Example 1 Emulsion Compound of the present invention 5 parts Xylene 70 parts N, N-dimethylformamide 20 parts Solpol 2680 5 parts (Mixture of nonionic surfactant and anionic surfactant: Toho The above is uniformly mixed to form an emulsion. For use, the above emulsion is diluted 50 to 20,000 times and dispersed so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 2 Water-dispersible compound of the present invention 25 parts Siglite PFP 66 parts (mixture of kaolinite and sericite; trade name of Siglite Industry Co., Ltd.) Sorpol 5039 ... 4 parts (anionic surfactant : Toho Chemical Industry Co., Ltd.) Carplex # 80 3 parts (white carbon: Shionogi & Co., Ltd. brand name) Calcium lignin sulfonate 2 parts And For use, the above wettable powder is diluted 50 to 20,000 times and dispersed so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 3 Oil Agent Compound of the present invention: 10 parts Methylcellosolve: 90 parts The above components are uniformly mixed to prepare an oil agent. At the time of use, the above oil agent is sprayed so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 4 Powder Compound of the present invention: 3.0 parts Carplex # 80: 0.5 part (white carbon: trade name of Shionogi & Co., Ltd.) Clay: 95 parts Diisopropyl phosphate: 1.5 parts To make a powder. When using the above powder, the active ingredient amount is 0.005 to 50 kg per hectare
Spray so that it becomes.

Formulation Example 5 Granules Compound of the present invention 5 parts Bentonite 54 parts Talc 40 parts Calcium ligninsulfonate 1 part The above are uniformly mixed and pulverized, and a small amount of water is added, followed by stirring and mixing. Granulate with a granulator and dry to obtain granules. When using the above granules, the active ingredient amount is 0.00 per hectare
Spray so that the weight is 5-50kg.

Formulation Example 6 Flowable agent Compound of the present invention 35 parts Solpol 3353 10 parts (nonionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) Lunox 1000C 0.5 parts (anionic surfactant: Toho Chemical Co., Ltd.) Industrial Co., Ltd. 1% xanthan gum aqueous solution 20 parts (natural polymer) water 34.5 parts The above components except for the active ingredient (compound of the present invention) are uniformly dissolved, and then the compound of the present invention is added. After stirring,
Wet pulverization with a sand mill to obtain a flowable agent. For use, the above-mentioned flowable is diluted 50 to 20,000 times and sprayed so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Production Example 7 Granular wettable powder Compound of the present invention ... 50 parts Clay ... 10 parts Ammonium sulfate ... 20 parts Sodium ligninsulfonate ... 10 parts Formalin condensate of naphthalenesulfonic acid ... 10 parts And kneaded with water
Granulation is carried out by an extrusion granulator equipped with a 0.5 mmφ screen, and moisture is dried to obtain a granular wettable powder. When used, the above granular water dispersible powder has an active ingredient content of 0.005 per hectare.
Sprinkle to ~ 50kg.

Next, the usefulness of the compound of the present invention as a pesticide will be specifically described in the following test examples.

Test Example 1 Insecticidal test against leafhopper leafhopper A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound) was diluted with water containing a spreading agent to give a chemical solution of 500 ppm concentration. Was adjusted.

This solution was sprayed on rice foliage planted in a 1/20000 are pot in a sufficient amount, and after air-drying, 20 larvae of the second instar larva of the green leafhopper, resistant to organophosphorus and carbamate insecticides, were released per pot. The insects were covered with a wire mesh cylindrical cage and stored in a constant temperature room.

The survey was carried out 30 days later, the number of parasites (surviving insects) of the leafhopper, Parasitoids persica, on each rice was investigated, and the mortality was calculated by the following formula. In addition, the test is 1 section 2
Performed in repetitions.

As a result, the following compounds showed a high effect of 100% mortality.

Compound No. of the present invention: 2, 3, 5, 6, 11, 19, 20, 31, 6
6, 67, 79, 80, 81, 120, 126, 128.

Test Example 2 Insecticidal test against brown planthopper The test was carried out in the same manner as in Test Example 1 except that the second-instar larva of brown planthopper was used instead of the second-instar larva of leafhopper, which is resistant to organophosphorus insecticides and carbamate insecticides. Was.

As a result, the following compounds showed a high effect of 100% mortality.

Compound No. of the present invention: 5, 6, 19, 20, 31, 32, 33, 34, 3
5, 38, 39, 40, 42, 43, 44, 52, 53, 54, 56, 57, 5
9, 61, 65, 66, 67, 68, 69, 70, 77, 79, 80, 81.

Test Example 3 Insecticidal test against Aspergillus oryzae A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder or 20% oil depending on the compound) was weighed into a transparent spict tube, and acetone was added thereto. A 500 ppm acetone solution was obtained. 10cc of this acetone solution
It was added to 10 g of wheat flour placed in a 9 cm petri dish, and after stirring, acetone was distilled off. The petri dish was then released with 10 adult males and females of the moss, and stored in a constant temperature room. The survey was conducted 90 days later, and the number of adult adults after the next generation was observed.

 In addition, the test was performed in 2 repetitions of 1 section.

As a result, for the following compounds, newly emerged adults were not observed at all.

Compound No. of the present invention: 1, 2, 3, 5, 6, 7, 8, 9, 1
0, 11, 19, 20, 21, 31, 32, 33, 34, 35, 38, 39, 4
0, 42, 43, 44, 45, 46, 47, 50, 54, 56, 57, 63, 6
4, 65, 66, 67, 68, 69, 75, 77, 79, 80, 81, 82.

Test Example 4 Insecticidal test against Culex pipiens 5% emulsion of the compound of the present invention described in the specification (25% wettable powder or 20% oil depending on the compound) was diluted with water to prepare a 10 ppm concentration drug solution. did.

This solution is applied to a waist high petri dish with a diameter of 9 cm and a height of 6 cm for 200 m.
Then, 10 larvae of Culex pipiens were released. This petri dish with high waist was stored in a constant temperature room at 25 ° C., and after 7 days, the number of adults that emerged was examined.

 In addition, the test was performed in 2 repetitions of 1 section.

As a result, for the following compounds, newly emerged adults were not observed at all.

Compound No. of the present invention: 1, 3, 5, 6, 7, 8, 9, 10, 1
1, 20, 21, 24, 26, 27, 28, 42, 43, 45, 46, 47, 5
0, 54, 57, 63, 64, 66, 75, 77, 79, 80, 81, 82, 12
8, 130, 132, 146.

Test Example 5 Insecticidal test against Streptococcus lactis 5% emulsion of the compound of the present invention described in the specification (25% wettable powder or 20% oil depending on the compound) was weighed into a transparent spit tube, and acetone was added. As a result, an acetone solution having a concentration of 500 ppm was obtained.

10 cc of this acetone solution was added to 10 g of rice bran in a petri dish having a diameter of 9 cm, and after stirring, acetone was distilled off. Then, ten petrels of the larvae of the mosquitoes were released into the petri dish and stored in a constant temperature room. The survey was performed 30 days later, and the number of adults was observed.

 In addition, the test was performed in 2 repetitions of 1 section.

As a result, for the following compounds, newly emerged adults were not observed at all.

Compound No. of the present invention: 1, 2, 3, 5, 6, 7, 8, 9, 1
0, 11, 19, 20, 21, 31, 32, 33, 34, 35, 36, 37, 3
8, 39, 42, 43, 44, 45, 46, 47, 49, 50, 52, 53, 5
4, 56, 57, 63, 64, 65, 66, 67, 68, 69, 70, 75, 7
7, 79, 80, 81, 82.

Test Example 6 Insecticidal test against Japanese moth moth A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder was used depending on the compound) was diluted with water containing a spreading agent to give a 500 ppm concentration. Adjusted to chemical solution.

The perilla leaves were immersed in this chemical solution, air-dried, and then placed in a petri dish having a diameter of 7 cm. Ten larvae of the third instar larva were released per petri dish and stored in a thermostatic chamber. The survey was carried out 20 days later, and the numbers of the emerged adults (the number of surviving insects) were examined, and the mortality was calculated by the same formula as in Test Example 1.

 In addition, the test was performed in 2 repetitions of 1 section.

As a result, the following compounds showed a high effect of a mortality of 100%.

Compound No. of the present invention: 1, 2, 3, 4, 5, 6, 11, 19, 2
0, 21, 31, 32, 33, 34, 35, 36, 37, 38, 39, 42, 4
3, 44, 45, 46, 47, 49, 50, 52, 53, 54, 56, 57, 6
3, 64, 65, 66, 67, 68, 69, 70, 75, 77, 79, 80, 8
1, 82.

Test Example 7 Insecticidal test against black elephant A 5% emulsion of the compound of the present invention described in the description (25% wettable powder was used depending on the compound) was diluted with water containing a spreading agent to give a 500 ppm concentration. Adjusted to chemical solution. In this medicine,
Immerse 10 g of brown rice in a 9 cm diameter petri dish, air-dry,
Ten adult males and females of the black elephant were released and stored in a constant temperature room.

The survey was conducted 90 days later, and the number of adult adults after the next generation was observed.

 In addition, the test was performed in 2 repetitions of 1 section.

As a result, for the following compounds, newly emerged adults were not observed at all.

Compound No. of the present invention: 1, 2, 3, 4, 5, 6, 7, 8,
9, 10, 11, 20, 21, 31, 32, 34, 35, 36, 38, 42, 4
3, 44, 45, 46, 47, 56, 57, 63, 64, 65, 66, 75, 7
7, 79, 82.

Test Example 8 Insecticidal Test Against German Cockroaches A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder or 20% oil depending on the compound) was weighed into a transparent spict tube, and acetone was added to add 500 ppm. A concentrated acetone solution was obtained.

10 cc of this acetone solution was added to a small animal powdered feed placed in a 9 cm diameter petri dish and stirred, and then acetone was distilled off. This petri dish was placed in a large petri dish having a diameter of 20 cm, and was used as a bait. Then, 10 large German cockroaches (5th-instar larvae) were released into this large petri dish and stored in a constant temperature room.

A petri dish containing absorbent cotton containing water was placed in a large petri dish to give water. The survey was performed 60 days later, and the number of adults was observed. In addition, the test was performed in 2 repetitions of 1 section.
As a result, the following compounds did not show adult appearance at all.

Compound No. of the present invention: 1, 2, 3, 4, 5, 6, 7, 8,
9, 10, 11, 19, 20, 21, 31, 32, 33, 34, 35, 36, 3
7, 38, 39, 40, 42, 43, 44, 45, 46, 47, 49, 50, 5
2, 53, 54, 56, 57, 75, 77, 79, 82.

Test Example 9 Insecticidal test against housefly A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder was used depending on the compound) was diluted with water to give 500 p.
The solution was adjusted to a pm concentration.

1 cc of the drug solution was dropped on a filter paper placed in a petri dish having a diameter of 9 cm. Then add 10 housefly terminal larvae to this petri dish.
The head was released and stored in a constant temperature room.

The survey was conducted two weeks later, and the number of emerged adults was examined. The test was performed in two repetitions per section.

As a result, the following compounds did not show adult appearance at all.

Compound No. of the present invention: 8, 9, 21, 42, 43, 45, 46, 47, 6
3, 65, 75, 82, 146.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 413/12 237 C07D 413/12 237 (72) Inventor Toshiro Miya 1470 Shirooka, Shirooka-cho, Minami-Saitama-gun, Saitama Nissan Chemical Industry Co., Ltd. Biological Science Research Institute (72) Inventor Hiroshi Haruyama 1470 Shirooka, Shirooka-cho, Shiraoka-cho, Minamisaitama-gun, Saitama Nissan Chemical Industry Co., Ltd.Examiner of the Biological Science Research Laboratory Shunichi Yokoo (56) Reference JP-A-2-32065 (JP, A) JP-A-1-250361 (JP, A) JP-A-1-199953 (JP, A) JP-A-62-123176 (JP, A) JP-A-61-130275 (JP, A) Patent 2674102 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07D 237/16 C07D 401/12 C07D 403/12 C07D 413/12 A01N 43/56 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound of the formula [I] [Wherein, R represents an alkyl group having 1 to 4 carbon atoms substituted by a cycloalkyl group having 3 to 8 carbon atoms, an alkyl group having 1 to 4 carbon atoms substituted by a phenyl group which may be substituted, R ¹ represents a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, or a hydroxy group substituted with a heterocyclic group which may be substituted; Or a haloalkyl group having 1 to 3 carbon atoms, provided that R ² , R
c, Rd and Re each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Rf represents a hydrogen atom or 1 to 4 carbon atoms.
X represents an alkyl group having 4 to 4 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group which may be substituted, or a heterocyclic group which may be substituted; S-, -NH- or (Rg represents an alkyl group having 1 to 4 carbon atoms);
1 represents a halogen atom, and Q represents an optionally substituted phenyl group, an optionally substituted naphthyl group, or an optionally substituted heterocyclic group. ｝ Represent. ] The 3 (2H) -pyridazinone derivative represented by these. 2. The 3 (2H)-according to claim (1).
A pest control agent comprising one or more pyridazinone derivatives as an active ingredient.