KR960012175B1 - Pyridazinone compounds derivative and composition for controlling and/or preventing insect pests - Google Patents

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Description

Pyridazinone derivatives and compositions for controlling pests

The present invention relates to novel pyridazinone derivatives and compositions for controlling pests. More specifically, the present invention relates to a novel 3 (2H) -pyridazinone derivative, a pesticidal, aphid and nematicidal composition containing the derivative as an active ingredient, and a true aphid parasitic composition parasitic in animals.

The invention is also associated with other patent applications. See EP-A-0088384, EP-A-0134439, EP-A-0183212, EP-A-0199281, EP-A-0210647, EP-A-0193853 and EP-A-0232825]. Known compounds described in these patent application publications are compounds of the following general formula (II).

Features of the compounds of formula (II) shown in the above patent application publications include, for example, some patent applications (EP-A-0088384, EP-A-0134439, EP-A-0183212, EP-A-0199281 and EP- A-0232825), Y 'is an oxygen atom or a sulfur atom, R' is an alkyl group, in another application (EP-A-0210647) R 'is an aryl group, and another application (EP-A-0193853 Is a nitrogen or oxygen atom, but R 'is a hydrogen atom or an alkyl group.

However, the compounds of the present invention are new compounds that are not included in the European Patent Application Publication.

On the other hand, Compound A of the following structural formula is known (see DT-OS-3328770).

In the above, compound A is only described as an intermediate compound, and the target compound derived from compound A is described as having agricultural bactericidal, insecticidal properties. However, the compound A is different from the compound (I) of the present invention in the following chemical structure and the action effect is different.

It is an object of the present invention to provide novel 3 (2H) -pyridazinone derivatives with insecticidal properties against insects, mites and nematodes.

Another object of the present invention is to provide a method for preparing the above 3 (2H) -pyridazinone derivative.

It is still another object of the present invention to provide an insecticidal, aphid and nematicidal composition containing at least one of the above 2 (2H) -pyridazinone derivatives as an active ingredient and a true aphid parasitic composition parasitic in animals.

It is another object of the present invention to provide a method for exterminating and / or preventing insects and other pests using the derivative or the composition.

Other objects of the present invention will be apparent from the following description.

The present invention is directed to insecticidal, aphid, and nematode compositions containing at least one of 3 (2H) -pyridazinone derivatives of the general formula (I) and derivatives thereof and to parasitic aphids parasitic in animals. It is about.

(I)

(I)

또는 시아노 그룹(여기서 Rb는 탄소 원자수 1 내지 4의 알킬 그룹)이고, Ra는 탄소 원자수 3 내지 16의 할로겐화 알킬렌 그룹, 탄소 원자수 2 내지 16의 할로겐화 알케닐렌 그룹, 탄소 원자수 2 내지 16의 할로겐화 알키닐렌 그룹, 탄소 원자수 3 내지 8의 할로겐화 시클로 알킬렌 그룹, 탄소 원자수 5 내지 8의 할로겐화 시클로 알케닐렌 그룹, 탄소 원자수 5 내지 8의 할로겐화 옥사시클로알킬렌 그룹, 탄소 원자수 5 내지 8의 할로겐화 티아시클로알킬렌 그룹, 탄소 원자수 3 내지 8의 시클로알킬 그룹과 할로겐 원자로 치환된 탄소 원자수 1 내지 4의 알킬렌 그룹, 옥시란 그룹과 할로겐 원자로 치환된 탄소 원자수 1 내지 4의 알킬렌 그룹, 치환 또는 비치환의 페닐 그룹과 할로겐 원자로 치환된 탄소 원자수 1 내지 4의 알킬렌 그룹이거나 치환 또는 비치환의 헤테로환 그룹(heterocyclic group)과 할로겐 원자로 치환된 탄소 원자수 1 내지 4의 알킬렌 그룹]이고 ; A는 수소 원자, 할로겐 원자, 탄소 원자수 1 내지 4의 알킬 그룹, 탄소 원자수 1 내지 4의 알콕시 그룹, 탄소 원자수 1 내지 4의 알킬티오 그룹, 탄소 원자수 1 내지 4의 알킬술피닐 그룹 또는 탄소 원자수 1 내지 4의 알킬술포닐 그룹이고 ; R¹은 수소 원자, 할로겐 원자, 탄소 원자수 1 내지 4의 알콕시 그룹 또는 히드록시 그룹이고 ; X는 산소 원자 또는 황 원자이고;

[위에서, R², Rc, Rd, Re 및 Rf는 각각 수소 원자, 산소 원자 또는 탄소 원자수 1 내지 4의 알킬 그룹이고, X¹은

(Rg는 탄소 원자수 1 내지 4의 알킬 그룹)이고, Hal은 할로겐 원자이고, Q는 치환된 페닐 그룹, 치환 또는 비치환의 나프틸 그룹이거나 치환 또는 비치환의 헤테로환 그룹이고, Q¹은 치환 또는 비치환의 페닐 그룹, 치환 또는 비치환의 나프틸 그룹이거나 치환 또는 비치환의 헤테로환 그룹]이다.In the above formula, R is an alkyl group of 3 to 8 carbon atoms substituted with an alkenyl group of 16 carbon atoms, an alkynyl group of 2 to 16 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, or G -Ra- [where G is a hydrogen atom,

Or a cyano group (where Rb is an alkyl group of 1 to 4 carbon atoms), Ra is a halogenated alkylene group of 3 to 16 carbon atoms, a halogenated alkenylene group of 2 to 16 carbon atoms, or 2 carbon atoms Halogenated alkynylene groups having from 16 to 16, halogenated cycloalkylene groups having from 3 to 8 carbon atoms, halogenated cyclo alkenylene groups having from 5 to 8 carbon atoms, halogenated oxacycloalkylene groups having from 5 to 8 carbon atoms, carbon atoms A halogenated thiacycloalkylene group having 5 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms substituted with a halogen atom, a carbon atom substituted with an oxirane group and a halogen atom 1 An alkylene group having 4 to 4, a substituted or unsubstituted phenyl group and an alkylene group having 1 to 4 carbon atoms substituted with a halogen atom, or a substituted or unsubstituted heterocyclic ring An alkylene group having 1 to 4 carbon atoms substituted with a heterocyclic group and a halogen atom; A is a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an alkylthio group of 1 to 4 carbon atoms, an alkylsulfinyl group of 1 to 4 carbon atoms Or an alkylsulfonyl group having 1 to 4 carbon atoms; R ¹ is a hydrogen atom, a halogen atom, an alkoxy group or hydroxy group having 1 to 4 carbon atoms; X is an oxygen atom or a sulfur atom;

[Wherein R ² , Rc, Rd, Re and Rf are each a hydrogen atom, an oxygen atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ is

(Rg is an alkyl group having 1 to 4 carbon atoms), Hal is a halogen atom, Q is a substituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted heterocyclic group, and Q ¹ is substituted or Unsubstituted phenyl group, substituted or unsubstituted naphthyl group, or substituted or unsubstituted heterocyclic group].

After a long and steady study, the inventors found that compounds of general formula (I) have excellent insecticidal properties against insects, ticks and nematodes.

For example, conventionally known compounds of the general formula (II) have a strong insecticidal effect against insects, ticks and nematodes, and the effect is quickly shown. On the other hand, the compound of the present invention has the action of inhibiting the transformation of insect pests, so the action effect is sustained gently. Moreover, the compounds of the present invention are effective against various kinds of pests even at low concentrations of drugs. Examples of these pests include hygiene harmful insects (Culex pipiens palens), blue rice cicada (Nephotettix cincticeps), brown rice cicada (Nilaparvata lugens), green peach grass (Myzus persicae), diamond beetle (Plutella xylostella) Stored agricultural pests such as Musca domestica, German cockroach (Blattella germanica), ants (Formicidae) and corn weevil, Sitophilus cryzae, Tribolium castaneum, Cadra cautella, and termites Insects, pests of animals, such as a mite, flea, and a mite, are mentioned.

In other words, the compounds of the present invention are Dictyoptera, Isoptera, Hemiptera, Lepidoptera, Coleoptera, Himenoptera, Dipthera. Diptera and mites and their eradication and prevention.

The effect is described in detail in the biological examples described below. In the substituent J of the general formula (I), when Q is an aryl group, J is a substituted phenyl group or a substituted or unsubstituted naphthyl group, and when Q ¹ is an aryl group, J is a substituted or unsubstituted phenyl group. Substituted or unsubstituted naphthyl group.

Examples of the substituent include halogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkyloxy group, alkenyloxy group, alkynyloxy group, methylenedioxy group, halogeno methylenedioxy group, alkylthio Group, alkenylthio group, alkylsulfinyl group, alkylsulfonyl group, cycloalkyloxy group, haloalkyl group, haloalkyloxy group, haloalkylthio group, alkylamino group, alkylcarbonylamino group, nitro group, sia Furnace group, hydroxyl group, alkylcarbonyl group, alkyloxycarbonyl group, carboxyl group, aryl group, aryloxy group, arylthio group, arylamino group, arylcarbonyl group, arylmethyleneoxy group, aryloxymethyl Group, arylmethylenecarbonyl group, substituted or unsubstituted pyridyloxy group, hydroxyalkyl group, alkylcarbonyloxyalkyl group, alkoxyalkyl group, alkyl A group such as O-alkyl, alkylcarbonyl-alkyl group, alkoxycarbonylalkyl group, cyanoalkyl group, a haloalkyl carbonyl group.

When Q or Q ¹ in the substituent J of the general formula (I) is a heterocyclic group, as a heterocyclic ring, for example, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, pyrazole, pyridine, pyridazine, pyrimidine , Pyrazine, benzoxazole, benzothiazole, benzothiophene, dibenzothiophene, benzofuran, benzimidazole, indole, indazole, quinoline, isoquinoline, quinoxaline and the like. The heterocyclic group may have a substituent, and examples of these substituents include halogen atom, alkyl group, alkoxy group, alkylthio group, alkylsulfonyl group, haloalkyl group, haloalkoxy group, nitro group, cyano group, alkylcar Carbonyl groups, phenyl groups, substituted aryl groups, and the like.

The compounds of the present invention can be prepared by various methods. Some examples of these methods are as follows.

Scheme (1)

(Method 1-a)

or

In the above Reaction Formulas (1), (2) and (3), R, A, R ¹ , X, X ¹ , Rc, Rd, Re, Rf, Q ¹ and J are as defined above, and Z ¹ is A halogen atom or an azole group, Z ² is a halogen atom, an akylsulfonate group or an arylsulfonate group, Z ³ is a halogen atom, R ³ is a compound having a double bond, and R ⁴ is a substituent having a reactive functional group .

In the schemes (1), (2) and (3), the solvents include lower alkanols (e.g. methanol, ethanol), ketones (e.g. acetone, methylethyl ketone), hydrocarbons (e.g. benzene, toluene). Ethers (e.g. isopropyl ether, tetrahydrofuran, 1,4-dioxane), amides (e.g. N, N-dimethylformamide, hexamethyl fogogric triamide), halogenated hydrocarbons (e.g. Dichloromethane, dichloroethane) and the like. If necessary, a mixed liquid of these solvents or a mixed liquid with water can be used.

Examples of the base include inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogen carbonate, and organic bases such as sodium methoxide, sodium ethoxide, triethylamine and pyridine. If necessary, quaternary ammonium salts such as triethylbenzylammonium chloride can be added to the reaction system as a catalyst. The reaction temperature is from -20 ° C to the boiling point of the solvent used in the reaction, preferably from -5 ° C to the boiling point of the solvent. The molar ratio of starting compound can be arbitrarily selected. However, it is preferable to use compounds of the same or similar molar ratio.

In the method (1-a) of Scheme (1), the compound of the general formula (1) of the present invention has Z ¹ of the compound of the general formula (III) in the presence of a base in an alcohol or thiol of the general formula (IV) It can be prepared by reaction under. Z ¹ is a halogen atom (preferably chlorine or bromine) and azoles (preferably 1-imidazole). The solvent used is N, N-dimethylformamide, methanol, ethanol, toluene or toluene-water mixture, and the like. As the base, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like can be used. As for reaction temperature, 20 degreeC-50 degreeC is preferable.

In the above reaction, the compound may be produced as a by-product, wherein the alcohol or thiol of the general formula (IV) is substituted at the 4-position of the pyridazinone ring. In this case, it is necessary to purify the target compound of the present invention by removing by-products. That is, if necessary, the product can be separated and purified by conventional methods such as recrystallization and column chromatography.

In the method (1-b), the compound of the present invention can be prepared by reacting a pyridazinone derivative of formula (V) with an alkylsulfonate or alkyl halide of formula (VI) in the presence of a base in a solvent. Z ² is preferably chlorine or bromine. As the solvent, N, N-dimethylformamide, methanol, ethanol, acetonitrile, toluene, toluene-water mixture, and the like can be used. As the base, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like can be used. Although reaction temperature is 20 degreeC-120 degreeC, when XH of the pyridazinone derivative of general formula (V) is OH, 20 degreeC-120 degreeC is preferable, and when XH is SH, 20 degreeC-50 degreeC is preferable. .

In the method (2-a) of Scheme (2), the compound of the present invention can be prepared by alkylating the 2-position of the pyridazinone derivative of the general formula (VII) with RZ ² of the general formula (VIII). In the above method, the compound of the present invention can be easily prepared by adding an inorganic base or an organic base to the reaction system to increase the reactivity of the pyridazinone derivative of the general formula (VII).

In the method (2-b) of Scheme (2), the compound of formula (I) of the present invention can be prepared by adding an N-halogenopyridazinone derivative of formula (IX) to the olefin of formula (X). Can be.

Method (2-b) is a suitable method for preparing the compound of general formula (I), and related art is disclosed in permanent patent No. 999,448.

Z ¹ is a halogen atom, particularly preferably chlorine, bromine or iodine. In this process, the compound of the general formula (I) of the present invention reacts a pyridazinone derivative of the general formula (IX) with an equal or excessive amount (10-fold molar) of olefin of the general formula (X) at -5 ° C to 120 ° C Can be prepared. The reaction proceeds well even when the reaction system is diluted with a solvent. Hydrocarbons as a solvent. Halogenated hydrocarbons, ketones, ethers and lower alcohols are preferred, and more preferably benzene, toluene, hexane, methylene chloride, chloroform, carbon tetrachloride, methyl ethyl ketone, methyl isobutyl ketone, isopropyl ether, 1, 4-dioxane, methanol, ethanol and the like can be used. When using olefins of general formula (X) having a low boiling point, good results can be obtained by using a pressurized reactor such as an autoclave.

The raw material N-halogenopyridazinone derivative can be manufactured by a well-known method (refer to German Patent No. 1,122,069) or an improved method thereof. Method (2-c) of Scheme (2) is obtained by converting the functional group of the N-substituent (R ⁴ ) of the pyridazinone derivative of the general formula (XI) to the chemically desired N-substituent (R). ) Is a method for producing the compound.

More specifically, the following method may be exemplified. A method of replacing a halogen atom contained in R ⁴ with a nucleophilic reagent (R'O-, R'S-, CN-, R'COO-, etc.); A method of ring-opening an oxirane group contained in R ⁴ with the nucleophilic reagent or electrophilic reagent (alkyl halide, Lewis acid reagent, etc.); A method of adding a halogen molecule to a double bond or a triple bond of R ⁴ ; Adding the nucleophilic reagent to a double bond adjacent to the electron withdrawing group contained in R ⁴ by a Michael form addition method; A method of converting a halogen atom of R ⁴ to hydrogen halide in the presence of a base and removing hydrogen halide from R ⁴ to form a double bond; A method of oxidizing an alcohol group of R ⁴ to an aldehyde group, a ketone group or a carboxyl group; Converting the double bond of R ⁴ to oxirane using an oxidizing agent; A method of reducing an aldehyde group, ketone group, carboxyl group or carboxylate group of R ⁴ with an alcohol; A method of leaving the halogen atom of R ⁴ ; Converting the alcohol group of R ⁴ to the corresponding halide using a halogenating agent; A method of converting an alcohol group and a halogen atom of R ^{4 into} an oxacycloalkyl group by intermolecular ring closure in the presence of a base; A method of converting a thiol group and a halogen atom of R ⁴ into a thiacycloalkyl group by intermolecular ring closure in the presence of a base.

In the method (3-a) of Scheme (3), the compound of Formula (III) may be reacted with a compound of Formula (XII) in a solvent in the presence of a base to prepare a compound of Formula (XIII). Meanwhile, the compound of the present invention is prepared by reacting the produced compound with an acid halide of a general formula (XIV) or a halide of a heterocyclic ring in the presence of a base.

Specific examples of the compounds within the scope of the present invention are shown in Tables 1, 1 and 3, but the scope of the present invention is not limited to the compounds in these tables.

In each table, Me is methyl, Et is ethyl, Pr is propyl, Bu is butyl, Pen is pentyl, Hex is hexyl, and Ph is unsubstituted phenyl, t is tertiary, and s is secondary ( secondary, i is iso and c is cyclo.

The compounds of the present invention contain asymmetric carbon atoms and therefore exist in the form of optically active (+) and (-) compounds, which are within the scope of the present invention.

On the other hand, the compounds of the present invention contain cis and trans compounds as geometric isomers.

A compound of formula

TABLE 1

A compound of formula

TABLE 2

A compound of formula

TABLE 3

In Tables 1, 2 and 3, Q 1 to Q 56 represent groups of the following structural formula.

Examples for the compounds of the present invention are specifically described below, which are not intended to limit the present invention.

Preparation Example 1

5- (4-t-butylbenzylthio) -4-chloro-2-[(2,2-dichloro-1,1-dimethyl) -ethyl] -3 (2H) -pyridazinone (Compound No. 2) Manufacture

0.73 g of 4,5-dichloro-2-[(2,2-dichloro-1,1-dimethyl) -ethyl] -3 (2H) -pyridazinone and 0.45 g of 4-t-butyl in 10 ml of methanol Benzyl-mercaptan was dissolved. The resulting solution was suspended with 0.27 g of sodium carbonate and stirred at room temperature for 3 hours. The solution was poured into iced water and filtered off. The obtained crystals were recrystallized from benzene-hexane to give 0.8 g of the target compound.

m.p. : 162 ℃ ~ 163 ℃

Preparation Example 2

Preparation of 4-bromo-5- (4-chloro-benzyloxy) -2-[(2,3-dichloro-2-methyl) -propyl] -3 (2H) -pyridazinone (Compound No. 12)

1.90 g of 4,5-dibromo-2-[(2,3-dichloro-2-dimethyl) -propyl] -3 (2H) -pyridazinone and 0.71 g in 10 ml of N, N-dimethylformamide 4-chlorobenzyl alcohol was dissolved. The solution was suspended with 0.33 g of powdered potassium hydroxide and the reaction mixture was stirred overnight at room temperature. The resulting solution was poured into iced water and extracted with benzene. The extract was washed sequentially with saturated brine and water and distilled under reduced pressure to remove the solvent. The oily product was separated and purified by silica gel column chromatography (eluent: chloroform) to yield 1.10 g of the target compound.

m.p. : 112 ℃ ~ 114 ℃

Preparation Example 3

Preparation of 2- (3'-bromopropyl) -4-chloro-5- (4'-chlorobenzyloxy) -3 (2H) -pyridazinone (Compound No. 19) of 150 ml of water and 150 ml of ethanol 22.3 g of 4,5-dichloro-2- (3'-hydroxypropyl) -3 (2H) -pyridazinone (0.1 mole) and 19.6 g of potassium hydroxide (0.35 mole) were added to the mixture and about 10 under reflux. Heated for hours. After the reaction, ethanol was distilled off under reduced pressure, water was added thereto, and the insoluble substance was filtered off.

The filtrate was acidified with dilute hydrochloric acid and the crystalline product was filtered off. The obtained crystals were washed with water and dried to give 14.5 g of 4-chloro-5-hydroxy-2- (3'-hydroxypropyl) -3 (2H) -pyridazinone.

10.2 g of 4-chloro-5-hydroxy-2- (3'-hydroxypropyl) -3 (2H) -pyridazinone (0.05 mole), 8.4 g of 4 in 150 ml of N, N-dimethylformamide -Chlorobenzyl chloride (0.052 mol) and 10.4 g of anhydrous potassium carbonate (0.075 mol) were added and heated at 100 DEG C-120 DEG C for 3 hours. After the reaction, the mixture was poured into water and extracted with ethyl acetate. The resulting solution was washed with water and then sequentially with 5% NaOH solution and saturated brine. The solution was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The solid product obtained was washed with n-hexane and dried to give 12.3 g of 4-chloro-5- (4'-chlorobenzyloxy) -2- (3'-hydroxypropyl) -3 (2H) -pyridazinone Obtained.

9.9 g of 4-chloro-5- (4'-chlorobenzyloxy) -2- (3'-hydroxypropyl) -3 (2H) -pyridazinone (0.03 mol) was added to 170 ml of chloroform, followed by 9.4 g of thionyl bromide (0.045 mol) was added slowly with stirring at -5 ° C to 5 ° C for 2 hours. After the reaction, water was added to the resulting solution little by little, the chloroform layer was separated, washed with water, and then sequentially washed with 5% sodium hydrogen carbonate solution and saturated brine. The solution was dried over anhydrous sodium sulfate and distilled under reduced pressure to remove the solvent. The solid product obtained was recrystallized from a mixed solvent of n-hexane-benzene to give 5.2 g of 2- (3'-bromopropyl) -4-chloro-5- (4'-chlorobenzyloxy) -3 (2H) -pyridine. Obtained dazinone.

m.p. : 83 ℃ ~ 87 ℃

Preparation Example 4

Preparation of 4-chloro-2 [(2-chloro-2-methyl) -pentyl] -5- (4-iodobenzyloxy) -3 (2H) -pyridazinone (Compound No. 33)

14.2 g of 4,5-dichloro-2-[(2-chloro-2-methyl) -pentyl] -3 (2H) -pyridazinone and 1.17 g of 4-iodobenzyl alcohol According to the method, 1.72 g of the target compound were obtained.

m.p. : 114 ℃ ~ 115 ℃

Preparation Example 5

4-Chloro-2-[(2,3-dichloro-2-methyl-propyl] -5-[(2-iodo-5-pyridyl) -methoxy] -3 (2H) -pyridazinone (Compound No. .202)

Prepared using 1.45 g of 4,5-dichloro-2- [2,3-dichloro-2-methyl) -propyl] -3 (2H) -pyridazinone and 1.18 g of 2-urido-5-pyridinmethanol According to the method of Example 2, 1.33 g of the target compound were obtained.

m.p. : 117 ℃ ~ 120 ℃

Preparation Example 6

Preparation of 4-chloro-2- (2-chloro-2-methylpropyl) -5- (2-phenoxy-ethoxy) -3 (2H) -pyridazinone (Compound No. 326)

To 10 ml of N, N-dimethylformamide, 1.85 g of 2- (2-chloro-2-methylpropyl) -4,5-dichloro-3 (2H) -pyridazinone and 1.00 g of 2-phenoxy ethanol Then, 0.48 g of powdered KOH was added. The mixture was stirred overnight at room temperature, and then the method of Preparation Example 2 was repeated to obtain 1.9 g of the target compound.

m.p. : 82 ℃ ~ 83 ℃

Preparation Example 7

Preparation of 5- (4-t-butyl-α-methylbenzyloxy) -4-chloro-2-vinyl-3 (2H) -pyridazinone (Compound No. 129)

2.7 g of 2- (2-bromoethyl) -4,5-dichloro-3 (2H) -pyridazinone and 1.8 g of 4-t-butyl-α-methyl in 60 ml of N, N-dimethylformamide -Benzyl alcohol was dissolved and then 1.4 g of powdered KOH was added. This solution was stirred overnight at room temperature.

After the reaction, the reaction mixture was poured into water and extracted with benzene. The benzene layer was washed with water, dried over anhydrous sodium sulfate, and then distilled under reduced pressure to remove the solvent. The viscous residual liquid was purified by silica gel column chromatography (eluate: mixture of benzene-ethyl acetate) to yield 2.2 g of the target compound.

¹ H-NMR (CDCl ₃ , δ, ppm) 1.37 (9H, s), 1.80 (3H, d, J = 6Hz), 4.95 (1H, d, J = 9Hz), 5.66 (1H, q, J = 6Hz ), 5.67 (1H, d, J = 15 Hz), 7.17 to 7.53 (4H, m), 7.68 (1H, d, d, J = 9 Hz, 15 Hz), 7.78 (1 H, s).

Preparation Example 8

Preparation of 4-chloro-2- (2-chloro-2-methylpentyl) -5- (4-ethylbenzyloxy) -3 (2H) -pyridazinone (Compound No. 85)

To 20 ml of N, N-dimethylformamide 1.2 g of 2- (2-chloro-2-methylpentyl) -4,5-dichloro-3 (2H) -pyridazinone and 0.64 g of 4-ethylbenzyl alcohol Then, 0.31 g of powder KOH was added under ice cooling, followed by stirring at room temperature for 1 hour. The method of Preparation Example 2 was repeated to yield 600 mg of the target compound.

m.p. : 81 ℃ ~ 83 ℃

Preparation Example 9

Preparation of 4-chloro-2- (2-chloro-2-methylpentyl) -5- (4-trifluoromethylbenzyloxy) -3 (2H) -pyridazinone (Compound No. 56)

1.2 g of 2- (2-chloro-2-methylpentyl) -4,5-dichloro-3 (2H) -pyridazinone and 0.78 g of 4-trifluoromethyl in 20 ml of N, N-dimethylformamide Benzyl alcohol was dissolved and then 1.46 g of anhydrous potassium carbonate was added. The mixture was stirred at 50 ° C. for 8 hours, and then the method of Preparation Example 2 was repeated to obtain 1.0 g of the target compound.

m.p. : 105 ℃ ~ 106 ℃

Preparation Example 10

4-Chloro-2- (2-chloro-2-methylpropyl) -5-[(2-iodo-5-pyridyl) -methoxy] -3 (2H) -pyridazinone and 4-chloro-5- Preparation of [(2-Udo-5-pyridyl) -methoxy] -2- (2-methyl-1-propenyl) -3 (2H) -pyridazinone (Compounds No. 237 and No. 255)

1.4 g of 2- (2-chloro-2-methylpropyl) -4,5-dichloro-3 (2H) -pyridazinone and 1.29 g of 2-ureido-5- in 10 ml of N, N-dimethylformamide Pyridyl methanol was dissolved and 0.33 g of powdered KOH was then added under ice cooling. The mixture was stirred at room temperature for one day, and then the method of Preparation Example 2 was repeated to 0.74 g of 4-chloro-2- (2-chloro-2-methylpropyl) -5-[(2-ureido-5-pyridyl) -Methoxy] -3 (2H) -pyridazinone (mp: 119 ° C-123 ° C) and 0.24 g of 4-chloro-5-[(2-iodo-5-pyridyl) -methoxy] -2- (2-Methyl-1-propenyl) -3 (2H) -pyridazinone (mp: 141 ° C to 142 ° C) was obtained.

Preparation Example 11

Preparation of 2- (2-chloro-2-methylpropyl) -5- (4-iodobenzyloxy) -4-methyl-3 (2H) -pyridazinone (Compound No. 167)

0.33 g of 5-chloro-2- (2-chloro-2-methylpropyl) -4-methyl-3 (2H) -pyridazinone and 0.33 g of 4-iodobenzyl in 5 ml of N, N-dimethylformamide The alcohol was dissolved and then 0.1 g of powdered KOH was added under ice cooling.

The method of Preparation Example 2 was repeated to yield 0.3 g of the target compound.

m.p. : 121 ℃ ~ 123 ℃

Preparation Example 12

Preparation of 4,5-dichloro-2- (3-chloro-tetrahydro-2-pyranyl) -3 (2H) -pyridazinone

4 g of 2,4,5-trichloro-3 (2H) -pyridazinone was dissolved in 20 ml of methylene chloride, and then 2.5 g of 2,3-dihydro-pyran was added dropwise under ice cooling. The solution was stirred for 30 minutes, and the resulting 4,5-dichloro-3 (2H) -pyridazinone was filtered off. The filtrate was distilled off under reduced pressure. The oily product thus obtained was purified and separated by silica gel column chromatography (eluent: benzene), and the first fraction of a trans-type compound (mp: 136 ° C to 137 ° C) was obtained from a second fraction of 1.5 g of a seed compound (mp: 109 ° C-110 ° C) 1.3 g were obtained.

¹ H-NMR (CDCl ₃ , δ, TMS)

Trans 1.50 ~ 2.20 (m, 4H), 3.50 ~ 4.60 (m, 3H), 5.86 (d, 1H, 10Hz), 7.77 (s.1H).

Seed type 1.90 ~ 2.50 (m, 4H), 3.50 ~ 4.60 (m, 3H), 6.05 (d, 1H, 3Hz), 7.83 (s.1H).

Preparation Example 13

Preparation of 4,5-dichloro-2- (2,3-dichloro-2-propenyl) -3 (2H) -pyridazinone

65 ml of N, N-dimethylformamide was added to a mixture of 10.8 g of 4,5-dichloro-3 (2H) -pyridazinone and 9.5 g of anhydrous potassium carbonate, followed by stirring at room temperature for 10 hours. Subsequently, 10.0 g of 1,2,3-trichloro-1-propene (a mixture of E-type and Z-type) was added to the mixed solution, and stirred at 40 ° C for 6 hours. The solution was poured into a large amount of water, extracted with benzene, distilled under reduced pressure to remove the solvent, and 6.0 g of the desired compound (a mixture of E-type and Z-type) was obtained. The obtained product was separated by silica gel column chromatography (eluent: benzene) to obtain an isomer (m.p.: 93.7 ° C-94.6 ° C, 112.8 ° C-114.8 ° C).

¹ H-NMR (CDCl ₃ , δ, TMS)

Isomer 1 (m.p.: 93.7 ℃ ~ 94.6 ℃): 5.15 (s, 2H), 6.47 (s, 1H), 7.84 (s, 1H)

Isomer 2 (m.p.: 112.8 ℃ ~ 114.8 ℃): 5.00 (s, 2H), 6.70 (s, 1H), 7.84 (s, 1H)

Preparation Example 14

Preparation of 4,5-dichloro-2- (2-methyl-2-propenyl) -3 (2H) -pyridazinone

10 g of 4,5-dichloro-3 (2H) -pyridazinone, 27 g of 3-chloro-2-methylpropene and 8.4 g of potassium carbonate were suspended in 50 ml of N, N-dimethylformamide.

The mixture was stirred at 40 ° C. for 5 hours, and then the method of Preparation Example 2 was repeated to obtain 4.9 g of the target compound.

m.p. : 52 ℃ ~ 54 ℃

Preparation Example 15

Preparation of 2- (2-chloro-2-methyl-propyl) -4,5-dichloro-3 (2H) -pyridazinone

5 g of 4,5-dichloro-2- (2-methyl-2-propenyl) -3 (2H) -pyridazinone and 0.1 g of trifluoromethyl ammonium chloride are dissolved in 100 ml of carbon tetrachloride, followed by 30 ml of concentrated hydrochloric acid was added. The mixture was stirred at room temperature for 3 days, then the organic layer was separated, washed with water, and dried over anhydrous sodium sulfate. The solution is evaporated under reduced pressure to yield 4.7 g of the desired compound.

m.p. : 61 ℃ ~ 66 ℃

The physical properties of the compounds prepared according to Preparation Examples 1-11 are shown in Tables 4, 5 and 6. In each table, Me is methyl, Et is ethyl, Pr is propyl, Bu is butyl, Pen is pentyl, Hex is hexyl, Ph is unsubstituted phenyl, t is tertiary, s is secondary, i Is iso and c represents cyclo.

The compound numbers listed in Tables 4, 5, and 6 may be referred to the above-described Production Examples and the Production Examples and Test Examples described later.

A compound of formula

TABLE 4

A compound of formula

TABLE 5

(*): TLC (silica gel: C ₆ H ₆ (10) -CH ₃ COOEt (1)) Rf / value = 0.15

(**): TLC (silica gel: C ₆ H ₆ (10) -CH ₃ COOEt (1)) Rf / value = 0.22

A compound of formula

TABLE 6

In Tables 4, 5 and 6, Q is the same as Q in Tables 1, 2 and 3.

When the compounds of the present invention are used in insecticidal, acaricidal and nematicidal compositions and true mite parasitic compositions parasitic in animals, they are usually suitable carriers such as solid carriers (e.g. clay, talc, bentonite or diatomaceous earth) or liquid carriers [ Examples: water, alcohols (e.g. methanol, ethanol), aromatic hydrocarbons (e.g. benzene, toluene, xylene), chlorinated hydrocarbons, ethers, ketones, esters (e.g. ethyl acetate) or acid amides ( Example: Dimethylformamide). If necessary, emulsifiers, dispersants, suspending agents, wetting agents, diffusing agents, stabilizers, and the like may be mixed to emulsifiable concentrations, emulsions, wettable powders, dusts, granules or floors. Formulated in the form of a flowable or the like.

Moreover, this mixing agent can mix and use other insecticide, fungicide, herbicide, plant growth regulator, medium hardener, etc. as needed.

The amount of the compound of the present invention as an active ingredient may vary from 0.005 kg to 50 kg per hectare, depending on the time and place of using the compound, the method of use, the insect to be killed and the resulting disease, and the grains.

Next, the kind and compounding ratio of a preparation are shown.

The above figures are in weight percent.

In use the emulsifiable concentrate, emulsion, flowable and wettable powder are diluted with a calculated amount of water. Dust and granules are used directly, without dilution with water, and the granules are contained in the feed.

The combination of each of the above components will be illustrated next.

Emulsifiable concentrate

Active Ingredients: Compounds of the Invention

Carriers: xylene, dimethylformamide, methylnaphthalene, cyclohexanone, dichlorobenzene, isophorone

Surfactant: Solpol 2680, Solpol 3005X, Solpol 3353

Other Ingredients: piperonylbutoxide, benzotriazole

Latex

Active Ingredients: Compounds of the Invention

Carriers: xylene, methyl cellosolve, kerosene

Flowable agent

Active Ingredients: Compounds of the Invention

Carrier: Water

Surfactants: Lunox 1000C, Solpol 3353, Soprophor FL, Nipol, Aggrisol S-7110, Sodium Lignin Sulfate

Other Ingredients: Xanthan Gum, Formalin, Ethylene Glycol, Propylene Glycol

Wettable powder

Active Ingredients: Compounds of the Invention

Carriers: Potassium Carbonate, Kaolinite, Zeeklite D, Ziclite PFP, Diatomite, Talc

Surfactant: Solpol 5039, Lunox 1000C, Calcium Lignin Sulfate, Sodium Dodecyl Benzenesulfonate, Solpol 5050, Solpol 005D, Solpol 5029-0

Other Ingredients: Carplex # 80

Dust

Active Ingredients: Compounds of the Invention

Carrier: Potassium Carbonate, Kaolinite, Zyclide D, Talc

Other Ingredients: Diisopropyl Phosphate, Carplex # 80

Granules (1)

Active Ingredients: Compounds of the Invention

Carriers: potassium carbonate, kaolinite, bentonite, talc

Other Ingredients: Calcium Lignin Sulfate, Polyvinyl Alcohol

Granules (2)

Active Ingredients: Compounds of the Invention

Carriers: Wheat flour, Bran, Grain corn, Ziclite D

Other Ingredients: Paraffin, Soybean Oil

Formulation examples of the composition comprising the compound of the present invention as an active ingredient in the insecticidal, acaricidal and nematicidal composition and the parasitic mite parasitic composition parasitic in animals are as follows. These formulation examples are only examples and do not limit the present invention.

In the following formulation examples parts are parts by weight.

Formulation Example 1: Emulsifiable Concentrate

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … chapter 1

Xylene… … … … … … … … … … … … … … … … … … … … … … … … … … … 75 copies

N, N-dimethylformamide... … … … … … … … … … … … … … … … … … … … Part 20

Solpole 2680 (brand name) (mixture of nonionic surfactant and anionic surfactant manufactured by Toho Chemical Co., Ltd., Japan). … … … … … … … … … … … … … … … … … Part 4

Formulation Example 2: Emulsifiable Concentrate

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … Part 5

Xylene… … … … … … … … … … … … … … … … … … … … … … … … … … … … 70 copies

N, N-dimethylformamide... … … … … … … … … … … … … … … … … … … … Part 20

Solpole 2680. … … … … … … … … … … … … … … … … … … … … … … … … … … Part 5

Formulation Example 3: Emulsifiable Concentrate

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … Part 10

Xylene… … … … … … … … … … … … … … … … … … … … … … … … … … … … 70 copies

N, N-dimethylformamide 5 parts

Solpole 2680. … … … … … … … … … … … … … … … … … … … … … … … … … Part 10

Piperonyl butoxide… … … … … … … … … … … … … … … … … … … … … … Part 5

Formulation Example 4: Emulsifiable Concentrate

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … Part 20

Xylene… … … … … … … … … … … … … … … … … … … … … … … … … … … … 50 copies

N, N-dimethylformamide 7 parts

Solpole 2680. … … … … … … … … … … … … … … … … … … … … … … … … … … Part Three

Piperonyl butoxide… … … … … … … … … … … … … … … … … … … … … … Part 20

Formulation Example 5: Emulsifiable Concentrate

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … Part 25

Xylene… … … … … … … … … … … … … … … … … … … … … … … … … … … … 50 copies

N, N-dimethylformamide... … … … … … … … … … … … … … … … … … … … … Part Two

Solpole 2680. … … … … … … … … … … … … … … … … … … … … … … … … … Part 20

Piperonyl butoxide… … … … … … … … … … … … … … … … … … … … … … Part Three

Each component of the emulsifiable concentrate is mixed evenly to prepare each emulsifiable concentrate. In use, the emulsifiable concentrate is diluted in water at a concentration of 1/250 or less, and the active ingredient per hectare is sprayed at a rate of 0.005 kg to 50 kg.

Formulation Example 6: Wettable Powder

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … chapter 1

XICLITE PFP (brand name) (mixture of kaolinite and sericite manufactured by XICLITE MINING INDUSTRIAL CO., LTD.). … … … … … … … … … … … … … … … … … Part 93

Solpol 5039 (brand name) (anionic surfactant manufactured by Toho Chemical Co., Ltd. of Japan). … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 4

Carplex # 80 (brand name) (white carbon made by Japanese Tono Pharmaceutical Co., Ltd.) … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … Part Two

Formulation Example 7: Wettable Powder

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … Part 10

ZyClite PFP… … … … … … … … … … … … … … … … … … … … … … … 80 copies

Solpol 5039. … … … … … … … … … … … … … … … … … … … … … … … … … … Part 6

Carplex # 80… … … … … … … … … … … … … … … … … … … … … … … … … Part 4

Formulation Example 8: Wettable Powder

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … Part 25

ZyClite PFP… … … … … … … … … … … … … … … … … … … … … … … Part 66

Solpol 5039. … … … … … … … … … … … … … … … … … … … … … … … … … … Part 4

Carplex # 80… … … … … … … … … … … … … … … … … … … … … … … … … Part Two

Lignin calcium sulfate… … … … … … … … … … … … … … … … … … … … … … … … Part Three

Formulation Example 9: Wettable Powder

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … 50 copies

ZyClite PFP… … … … … … … … … … … … … … … … … … … … … … Part 47

Solpol 5039. … … … … … … … … … … … … … … … … … … … … … … … … … Part Two

Carplex # 80… … … … … … … … … … … … … … … … … … … … … … … … … chapter 1

Formulation Example 10 Wettable Powder

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … 70 copies

ZyClite PFP… … … … … … … … … … … … … … … … … … … … … … Part 15

Solpol 5039. … … … … … … … … … … … … … … … … … … … … … … … … … Part 6

Carplex # 80… … … … … … … … … … … … … … … … … … … … … … … … … Part 4

Lignin calcium sulfate… … … … … … … … … … … … … … … … … … … … … … … … Part 5

The components of each wettable powder are intimately mixed and then ground to prepare each wettable powder. In use, the wettable powder is diluted in water at a concentration of 1/250 or less and sprayed at a rate of 0.005 kg to 50 kg of active ingredient per hectare.

Formulation Example 11 Latex

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … chapter 1

Methyl cellosolve... … … … … … … … … … … … … … … … … … … … … … … … … Part 99

Formulation Example 12 Latex

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … Part 20

Methyl cellosolve... … … … … … … … … … … … … … … … … … … … … … … … … 80 copies

Formulation Example 13 Latex

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … Part 30

Methyl cellosolve... … … … … … … … … … … … … … … … … … … … … … … … … 70 copies

The emulsion is prepared by evenly mixing the respective emulsion components. When used, latex is applied at a rate of 0.005 kg to 50 kg of active ingredient per hectare.

Formulation Example 14 Dust

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … 0.01 part

Carplex # 80 (brand name) (white carbon made by Japanese Tono Pharmaceutical Co., Ltd.)… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 0.1 part

Clay… … … … … … … … … … … … … … … … … … … … … … … … … Part 99.5

Diisopropyl phosphate… … … … … … … … … … … … … … … … … … … 0.39part

Formulation Example 15 Dust

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … 0.1 part

Carplex # 80… … … … … … … … … … … … … … … … … … … … … … … … 0.1 part

Clay… … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 99.5

Diisopropyl phosphate… … … … … … … … … … … … … … … … … … … 0.3 part

Formulation Example 16 Dust

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … chapter 1

Clay… … … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 99

Formulation Example 17 Dust

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … Part 10

Carplex # 80… … … … … … … … … … … … … … … … … … … … … … … … 0.2 part

Clay… … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 89

Diisopropyl phosphate… … … … … … … … … … … … … … … … … … … 0.8 part

Formulation Example 18 Dust

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … Part 30

Carplex # 80… … … … … … … … … … … … … … … … … … … … … … … … chapter 1

Clay… … … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 67

Diisopropyl phosphate… … … … … … … … … … … … … … … … … … … … Part Two

Dust is prepared by mixing the dust ingredients evenly. When used, dust is sprayed at a rate of 0.005 kg to 50 kg of active ingredient per hectare.

Formulation Example 19 Granules (1)

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … 0.01 part

Bentonite… … … … … … … … … … … … … … … … … … … … … … … … … Part 59.5

Talc… … … … … … … … … … … … … … … … … … … … … … … … … … … … 40 copies

Lignin calcium sulfate… … … … … … … … … … … … … … … … … … … … … … 0.49part

Formulation Example 20 Granules (1)

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … 0.5 part

Bentonite… … … … … … … … … … … … … … … … … … … … … … … … … Part 59.5

Talc… … … … … … … … … … … … … … … … … … … … … … … … … … … … 40 copies

Formulation Example 21 Granules (1)

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … chapter 1

Bentonite… … … … … … … … … … … … … … … … … … … … … … … … … … 40 copies

Talc… … … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 51

Lignin calcium sulfate… … … … … … … … … … … … … … … … … … … … … … … … Part 8

Formulation Example 22 Granules (1)

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … Part 5

Bentonite… … … … … … … … … … … … … … … … … … … … … … … … … … Part 54

Talc… … … … … … … … … … … … … … … … … … … … … … … … … … … … … 40 copies

Lignin calcium sulfate… … … … … … … … … … … … … … … … … … … … … … … … chapter 1

Formulation Example 23 Granules (1)

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … Part 30

Bentonite… … … … … … … … … … … … … … … … … … … … … … … … … … Part 37

Talc… … … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 30

Lignin calcium sulfate… … … … … … … … … … … … … … … … … … … … … … … … Part Three

The components of the granules 1 are intimately mixed and pulverized, and then a small amount of water is added and mixed with stirring. The mixture is extruded granulated with an extruder granulator and dried to prepare granules. In use, the granules are sprayed at a rate of 0.005 kg to 50 kg of active ingredient per hectare.

Formulation Example 24 Granules (2)

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … 0.01 part

flour … … … … … … … … … … … … … … … … … … … … … … … … … … Part 49.5

Bran… … … … … … … … … … … … … … … … … … … … … … … … … … … … 50 copies

Soybean oil… … … … … … … … … … … … … … … … … … … … … … … … … … … 0.49part

Formulation Example 25 Granules (2)

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … 0.5 part

flour … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 49.5

Bran… … … … … … … … … … … … … … … … … … … … … … … … … … … … 50 copies

Formulation Example 26 Granules (2)

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … chapter 1

flour … … … … … … … … … … … … … … … … … … … … … … … … … … … … 40 copies

Bran… … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 51

Soybean oil… … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 4

Paraffin… … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 4

Formulation Example 27 Granules (2)

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … Part 5

flour … … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 44

Bran… … … … … … … … … … … … … … … … … … … … … … … … … … … … 50 copies

Soybean oil… … … … … … … … … … … … … … … … … … … … … … … … … … … … chapter 1

Formulation Example 28 Granules (2)

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … Part 30

flour … … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 27

Bran… … … … … … … … … … … … … … … … … … … … … … … … … … … … 40 copies

Soybean oil… … … … … … … … … … … … … … … … … … … … … … … … … … … … Part Three

Each granule component is intimately mixed to prepare granules (2). In use, the granules are sprayed at a rate of 0.005 kg to 50 kg of active ingredient per hectare.

Formulation Example 29: Flowable Agent

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … chapter 1

Solpole 3353 (brand name) (nonionic surfactant from Toho Chemical Co., Ltd., Japan). … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 0.9 part

Runox 1000C (brand name) (anion surfactant from Toho Chemical Co., Ltd.) … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 0.1 part

1% xanthan gum aqueous solution (natural polymer compound). … … … … … … … … … … … Part 8

Water… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 90 copies

Formulation Example 30: Flowable Agent

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … Part 15

Solpole 3353. … … … … … … … … … … … … … … … … … … … … … … … … … Part 15

Runox 1000C… … … … … … … … … … … … … … … … … … … … … … … … … Part 5

Water… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 65 copies

Formulation Example 31: Flowable Agent

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … Part 35

Solpole 3353. … … … … … … … … … … … … … … … … … … … … … … … … … Part 14

Runox 1000C… … … … … … … … … … … … … … … … … … … … … … … … … chapter 1

1% xanthan gum aqueous solution... … … … … … … … … … … … … … … … … … … … … … Part 10

Water… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 45

Formulation Example 32: Flowable Agent

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … 50 copies

Solpole 3353. … … … … … … … … … … … … … … … … … … … … … … … … … … Part 9

Runox 1000C… … … … … … … … … … … … … … … … … … … … … … … … … chapter 1

1% xanthan gum aqueous solution... … … … … … … … … … … … … … … … … … … … … … Part 10

Water… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 30

Formulation Example 33: Flowable Agent

Compound of the Invention … … … … … … … … … … … … … … … … … … … … … … … 70 copies

Solpole 3353. … … … … … … … … … … … … … … … … … … … … … … … … … … Part 9

Runox 1000C… … … … … … … … … … … … … … … … … … … … … … … … … chapter 1

1% xanthan gum aqueous solution... … … … … … … … … … … … … … … … … … … … … … Part 10

Water… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … Part 10

Each component of the flowable agent except the active ingredient (compound of the present invention) is mixed evenly to form a mixed solution. Components are added to the mixed solution and stirred, followed by wet grinding with a sand mill to prepare a flowable. In use, the fluid is diluted with water to a concentration of less than 1/50 1 / 20,000 and sparged at a rate of 0.005 kg to 50 kg of active ingredient per hectare.

The pesticidal effects on the compounds of the present invention are specifically described in the following test examples.

Test Example 1

Insecticidal test on Nephotettix cincticeps

A 5% emulsifiable concentrate (or 25% wettable powder) of the compound of the present invention was diluted with water containing a diffusing agent to prepare a solution of 500 ppm of compound content.

The second age of blue rice cicada larvae resistant to organic insecticides and carbamate insecticides is sufficiently sprayed with the preparation solution on the stems and leaves of rice planted in 1 / 20,000 ar (pot). Viii) 20 larvae were released into the pot.

Ports treated as above were covered with a cylindrical wire gauze and placed in a thermostat. After 30 days left, the parasitic blue cicada larvae were examined and the lethality was calculated according to the following formula.

Contents

Each test compound was tested twice. As a result of the test, the following compound showed a high effect of 100% mortality.

Compound no. 9, 10, 12, 15, 17, 19, 24, 25, 27, 28, 32, 33, 38, 39, 45, 49, 50, 52, 53, 75, 76, 77, 78, 80, 81, 85, 87, 92, 97, 104, 105, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 120, 122, 124, 125, 126, 127, 155, 156, 201, 202, 203, 204, 206, 207, 208, 209, 211, 212, 218, 219, 226, 228, 229, 230, 231, 234, 236, 237, 238, 239, 240, 244, 245, 247, 250, 251, 314, 321, 324, 325.

Test Example 2

Insecticidal Test on Brown Rice Cicada (Nilaparvata lugens)

The brown rice cicada larvae of the second age was used in place of the above Prunun rice cicada larvae resistant to organophosphorus and carbamate insecticides, and the method of Test Example 1 was repeated. As a result of the experiment, the following compound showed a high effect of 100% mortality.

Compound no. 11, 25, 34, 48, 93, 201, 202, 203, 204, 205, 207, 208, 209, 211, 212, 214, 215, 219, 228, 229, 230, 231, 234, 236, 237, 238, 239, 240, 243, 244, 245, 246, 247, 249, 250, 251, 254, 255, 256, 257, 259, 263, 264, 265, 271, 302.

Test Example 3

Insecticidal test on red powder beetle (Tribolium castaneum)

A 500% acetone solution with a compound content of 500 ppm was prepared by adding a 5% emulsifiable concentrate (or 25% wettable powder or 20% emulsion) of the compound of the present invention in a clear small test tube and adding acetone. 10 g of wheat flour was placed in a 9 cm diameter laboratory dish, and 10 cc of the acetone solution was added thereto. Stir the mixture sufficiently to evaporate the acetone. Ten red powder beetles female and male adults were placed in a dish and left in a constant temperature room.

After 90 days, the expression adult number was counted to evaluate the effect. Twice each test compound was tested.

As a result of the test, no adult was expressed in the following compounds.

Compound no. 9, 10, 12, 15, 19, 24, 25, 32, 33, 39, 70, 71, 75, 76, 77, 78, 79, 80, 81, 84, 85, 86, 87, 92, 93, 94, 95, 97, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 155, 156, 159, 160, 161, 163, 164, 168, 169, 173, 201, 202, 203, 204, 206, 207, 208, 209, 211, 212, 226, 227, 228, 229, 230, 231, 232, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 255, 257, 263, 264, 266, 271.

Test Example 4

Insecticidal test for Culex pipiens pallens

5% emulsifiable concentrate (or 25% wettable powder or 20% emulsion) of the compound of the present invention was diluted with demineralized water to prepare a solution having a compound content of 10 ppm.

200 ml of the preparation solution was poured into a large test dish of 9 cm diameter and 6 cm height. 10 collecting larvae were placed in a plate and left in a constant temperature room at 25 ° C.

The dead larvae were examined after 7 days. Each test compound was tested twice.

As a result of the test, there were no remaining adults in the following compounds.

Compound no. 1, 2, 3, 4, 5, 6, 9, 10, 12, 14, 15, 17, 18, 19, 24, 25, 27, 28, 30, 32, 34, 35, 38, 39, 45, 49, 52, 53, 70, 71, 72, 73, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 90, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101 102, 103, 104, 105, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 122 , 123, 124, 125, 126, 127, 155, 156, 158, 160, 163, 164, 168, 169, 173, 201, 202, 203, 204, 205, 206, 207, 208, 209, 211, 212 , 215, 217, 218, 219, 224, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, 236, 237, 238, 239, 240, 241, 242, 244, 245, 246 , 250, 251, 255, 257, 264, 266, 301.

Test Example 5

Insecticidal test for tonsil moths (Cadra cautella)

A 5% emulsifiable concentrate (or 25% wettable powder or 20% emulsion) of the compound of the present invention was placed in a small transparent test tube to add acetone to prepare a 500 ppm acetone solution. 10 g of rice bran was placed in a 9 cm diameter test dish, and 10 cc of acetone solution was added thereto. The mixture was stirred sufficiently to evaporate acetone, and then 10 larvae of one-way moths were placed in a plate and left in a constant temperature room.

After 30 days, the remaining adults were examined to evaluate the effect. Twice each test compound was tested.

As a result of the test, there was no expression adult in the dish treated with the following compound.

Compound no. 9, 10, 11, 12, 15, 19, 24, 25, 27, 28, 32, 33, 34, 38, 39, 52, 53, 70, 71, 73, 74, 75, 76, 77, 78, 79, 80, 81, 84, 85, 86, 87, 89, 90, 92, 93, 94, 95, 97, 98, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 124, 125, 126, 127, 155, 156, 160, 162, 163, 164, 166, 167, 168, 169, 171, 172, 173, 201, 202, 203, 204, 206, 207, 208, 209, 211, 212, 214, 215, 217, 218, 219, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 249, 250, 251, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 266, 268, 270, 271, 302, 314, 318, 319.

Test Example 6

Insecticidal test on blue peach aphid (Myzus perciae)

A 5% emulsifiable concentrate (or 25% wettable powder) of the compound of the present invention was diluted with water containing a diffusing agent to prepare a solution of 500 ppm of compound content.

Each was placed in a 3 cm diameter test dish containing a paper soaked with a disc of the Cabsica oleracea leaf, and then 5 blue peach aphid larvae of the third age were released to each test dish and sprayed with a nebulizer.

The test dish was left in a constant temperature room, and the green peach grass water surviving after 7 days was examined, and lethality was calculated according to the formula of Test Example 1.

The test results showed a high effect of 100% mortality on the following compounds.

Compound no. 9, 10, 12, 15, 25, 27, 28, 32, 33, 34, 36, 37, 38, 39, 54, 55, 56, 58, 59, 61, 62, 64, 75, 76, 84, 85, 87, 93, 95, 96, 97, 100, 101, 102, 103, 104, 105, 107, 108, 110, 111, 115, 116, 118, 119, 120, 123, 124, 125, 126, 156, 159, 160, 161, 163, 164, 165, 167, 168, 169, 170, 173, 201, 202, 203, 204, 207, 208, 209, 211, 212, 215, 228, 231, 234, 244, 245, 246, 247, 250, 251, 255, 257, 259, 260, 261, 262, 264, 265, 266, 268, 270, 271, 301, 302, 303, 305, 306, 307, 310, 314, 318, 319, 320, 321.

Test Example 7

Insecticidal test on Plutella xylostella

A 5% emulsifiable concentrate (or 25% wettable powder) of the compound of the present invention was diluted with water containing a diffusing agent to prepare a solution of 500 ppm of compound content.

Cabbage (Brassica oleracea) leaves were immersed in the solution, dried, and placed in a test dish having a diameter of 7 cm. Ten larvae of diamond-backed moths of the third age were released in a test dish and left in a constant temperature room.

After 30 days, the expression adult was examined and the lethality was calculated according to the formula of Test Example 1. Twice each test compound was tested.

The test results showed a high effect of 100% mortality on the following compounds.

Compound no. 9, 10, 11, 12, 15, 17, 19, 24, 25, 27, 28, 32, 33, 34, 38, 39, 80, 81, 85, 104, 105, 118, 119, 124, 125, 127, 155, 156, 201, 202, 203, 204, 206, 207, 211, 212, 214, 215, 230, 231, 234, 236, 237, 243, 244, 245, 246, 247, 249, 250, 251, 255, 256, 257, 263, 264, 265, 271.

Test Example 8

Insecticidal test on corn weevil (Sitophilus oryzae)

A 5% emulsifiable concentrate (or 25% wettable powder) of the compound of the present invention was diluted with water containing a diffusing agent to prepare a solution of 500 ppm of compound content.

10 g of unmilled rice was placed in a test dish, sufficiently wetted with the solution, dried, and released from corn weevil adult females and 10 males. The test dish was left in the thermostat and after 90 days the expression adult number was examined and the efficacy was evaluated. Twice each test compound was tested.

As a result of the test, there was no expression adult in the test dish treated with the following compound.

Compound no. 24, 33, 62, 85, 100, 104, 106, 109, 115, 116, 118, 119, 120, 155, 160, 164, 165, 168, 203, 205, 206, 207, 211, 212, 228, 231, 237, 239, 240, 243, 244, 245, 246, 247, 249, 257, 264, 266.

Test Example 9

Insecticidal test for the German aphid (Blattella germanica)

A 5% emulsifiable concentrate (or 25% wettable emulsion) of the compound of the present invention was placed in a clear small test tube to add acetone to prepare acetone solution with a compound content of 500 ppm.

10 cc of acetone solution was mixed with 10 g of powdered feed (for small animal breeding) and placed in a test dish having a diameter of 9 cm. Stir the mixture sufficiently to evaporate the acetone. This test dish was placed in another large test dish of 20 cm in diameter. Ten large fifth-generation German aphid larvae were released into a large test dish. Large test dishes were left in the thermostat. A test dish with wet sanitary cotton was placed in a large test dish to water the larvae.

After 60 days, the expression adult was examined and evaluated for efficacy. Twice each test compound was tested.

As a result of the test, there was no expression adult in the test dish treated with the following compound.

Compound no. 201, 202, 203, 204, 206, 207, 211, 212, 230, 236, 237, 239, 243, 244, 245, 246, 247, 250, 251, 257, 265, 266.

Claims (12)

3 (2H) -pyridazinone compound of formula (I).

(I) In the above general formula, R is an alkyl group having 3 to 6 carbon atoms substituted with 1 to 3 halogen atoms; A is a halogen atom; R ¹ is a hydrogen atom; X is an oxygen atom or a sulfur atom; J is -CH ₂ -Q or

[Wherein R ² is a hydrogen atom or a methyl group and Q is

or

Wherein Y is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and a halo having 1 to 4 carbon atoms Selected from the group consisting of alkoxy groups). Insecticidal, aphid, and nematode compositions and parasitic aphids parasitic in animals, characterized by containing a 3 (2H) -pyridazinone compound of the general formula (I) as an active ingredient.

(I) In the above general formula, R is an alkyl group having 3 to 6 carbon atoms substituted with 1 to 3 halogen atoms; A is a halogen atom; R ¹ is a hydrogen atom; X is an oxygen atom or a sulfur atom; J is -CH ₂ -Q or

[Wherein R ² is a hydrogen atom or a methyl group and Q is

or

Wherein Y is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and a halo having 1 to 4 carbon atoms Selected from the group consisting of alkoxy groups). The 3 (2H) -pyridazinone compound according to claim 1, wherein the compound has the following structural formula.

The 3 (2H) -pyridazinone compound according to claim 1, wherein the compound has the following structural formula.

The 3 (2H) -pyridazinone compound according to claim 1, wherein the compound has the following structural formula.

The 3 (2H) -pyridazinone compound according to claim 1, wherein the compound has the following structural formula.

The 3 (2H) -pyridazinone compound according to claim 1, wherein the compound has the following structural formula.

The 3 (2H) -pyridazinone compound according to claim 1, wherein the compound has the following structural formula.

The 3 (2H) -pyridazinone compound according to claim 1, wherein the compound has the following structural formula.

The 3 (2H) -pyridazinone compound according to claim 1, wherein the compound has the following structural formula.

The 3 (2H) -pyridazinone compound according to claim 1, wherein the compound has the following structural formula.

The 3 (2H) -pyridazinone compound according to claim 1, wherein the compound has the following structural formula.