JP2685932B2 - Pyrazole oxime derivative and insecticide / miticide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a novel pyrazole oxime derivative and an insecticidal and acaricidal agent containing the derivative as an active ingredient.

The compounds of the present invention are also useful as synthetic intermediates for insecticides and acaricides.

[Structure of the Invention] (Means for Solving the Problems) The inventors of the present invention have conducted extensive studies as a result of obtaining a compound having excellent insecticidal and acaricidal activity, and as a result, the compound (I) represented by the general formula described below. Found that the insecticidal and acaricidal effects were extremely excellent, and completed the present invention.

The present invention has the general formula [In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, R ² represents an alkyl group having 1 to 5 carbon atoms, n represents 1 to 3, n is 2 or When representing 3, R ² may be the same or different. A represents an alkylene group having 1 to 5 carbon atoms] and an insecticidal and acaricidal agent containing the compound as an active ingredient.

In the above formula (I), the alkyl group having 1 to 5 carbon atoms is a linear or branched alkyl group, and is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl. , Amyl, isoamyl, and sec-amyl.

Halogen atoms include fluorine, chlorine, bromine and iodine.

The alkylene group having 1 to 5 carbon atoms is a linear or branched alkylene group such as methylene, ethylene, trimethylene, 1-methylethylene, 2-methylethylene, tetramethylene, dimethylmethylene and pentamethylene. Is mentioned.

 Preferred groups in formula (I) are as follows.

R ¹ is preferably a hydrogen atom or a methyl group.

R ² is preferably a methyl group or an ethyl group.

 A is preferably a methylene group or an ethylene group.

 n is preferably 1.

As can be understood from the above formula (I), the compound of the present invention has stereoisomers of E-form (syn-form) and Z-form (anti-form), but each of E-form, Z-form and mixtures thereof. Are also included in the present invention, and optical isomers based on the asymmetric carbon are also included in the present invention.

The compound (I) of the present invention can be easily produced, for example, by the method shown below.

Manufacturing method 1 (In the formula, R ¹ , R ² , A and n have the same meanings as described above, and Y represents a leaving group.) Examples of the leaving group of Y include a halogen atom such as chlorine, bromine or iodine. An alkanesulfonyloxy group which may be substituted with a halogen atom such as methanesulfonioxy, ethanesulfonyloxy or trifluoromethanesulfonyloxy; an arenesulfonyloxy group such as benzenesulfonyloxy or p-toluenesulfonyloxy. Can be mentioned.

As is clear from the above reaction formula, in this reaction, the compound H
Since -Y is eliminated, it is preferable to react in the presence of a base in order to capture this and smoothly react.

The reaction is usually carried out in the presence of a solvent, but the compounds of formula (II) and formula (III) can also be heated and reacted without a solvent.

The solvent is not particularly limited as long as it is not directly involved in this reaction, and for example, benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, Chlorinated or non-chlorinated aromatic, aliphatic or alicyclic hydrocarbons such as trichloroethylene and cyclohexane; ethers such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane; methanol, ethanol, i- Alcohols such as propanol, t-butanol, monoglyme, dilime;
Ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; N, N-dimethylformamide (DM
F), amides such as N, N-dimethylacetamide (DMA) and 1,3-dimethylimidazolidinone (DMI); dimethyl sulfoxide (DMSO); organics such as pyridine and N, N-dimethylaniline Base; a mixture of water and the above solvent.

When reacting in a biphasic mixed solvent, triethylbenzylammonium chloride or bromide,
It is preferable to use a phase transfer catalyst such as tetrabutylammonium chloride or bromide, trioctylmethylammonium chloride.

As the base, triethylamine, pyridine, N, N-
Examples thereof include organic bases such as dimethylaniline, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, inorganic bases such as sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.

The reaction temperature is not particularly limited, but it is usually at room temperature or higher and not higher than the boiling point of the solvent used, and heating may be performed to shorten the reaction time.

The starting material (II) used in this reaction is a known method such as C.I.
A.1970. 73 formylated product was synthesized by the method described in .3844w (I
It can be easily manufactured from V) as follows.

The raw material (III) can be easily produced by the method shown below.

(In the formula, R ¹ , R ² , A, n and Y are as defined above.) Production method 2 (In the formula, R ¹ , R ² , A and n have the same meanings as above.) The reaction is usually carried out in the presence of a solvent, but the compound of the formula (IV) and the formula (VI) are heated without a solvent. It can also be reacted. As the solvent, those described above can be used.

The starting material (VI) used in this reaction can be easily produced by a method known per se as shown below.

Manufacturing method 3 (In the formula, R ¹ , R ² , A, n and Y have the same meanings as described above.) As is clear from the above reaction formula, the compound H is also used in this reaction.
Since —Y is released, the solvent, base and the like shown in Production method 1 can be preferably used.

The target product (I) obtained by the above method can be appropriately purified by a known means such as recrystallization or various chromatography.

The compound (I) of the present invention is also useful as a production intermediate, and the compound (IX) having insecticidal, acaricidal and bactericidal activity can be easily produced by the method shown by the following reaction formula.

(In the formula, R ¹ , R ² , A and n are the same as defined above, and R ³ represents a hydrogen atom, a lower alkyl group or a halogen atom.) The compound (I) of the present invention is a hemiptera, for example, planter ,
Leafhoppers, aphids, and whiteflies: Lepidoptera, for example, Weevils, diamondback moths, leaf beetles, leaf moths,
It shows excellent insecticidal and acaricidal effects against agro-horticultural pests such as cabbage butterfly; Coleoptera, for example, weevils, beetles and the like;

It is also effective for controlling hygienic pests such as flies, mosquitoes, and cockroaches, and is also effective for other storage shell pests.

Furthermore, the compound (I) of the present invention is also effective against root-knot nematodes, pine wood nematodes, and mite in soil.

In addition, the compound (I) of the present invention is also effective against agricultural and horticultural diseases, and shows activity against, for example, rice blast disease, barley powdery mildew, cucumber downy mildew, cucumber gray mold, and tomato epidemic.

Thus, the compound (I) of the present invention has a very wide range of uses and application scenes, high efficacy, and can be put to practical use in various dosage forms.

The insecticidal and acaricidal agent of the present invention contains one or more compounds of the general formula (I) as an active ingredient. Although the compound of the general formula (I) may be used as such, it is usually mixed with an ordinary carrier, a surfactant, a dispersant or an auxiliary agent, and then, for example, a powder, a wettable powder, an emulsion. , Granules,
It is used by preparing it into a composition such as granules, water or oily suspension, and aerosol.

Suitable carriers are, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea; hydrocarbons such as kerosene and mineral oil; benzene, toluene, Aromatic hydrocarbons such as xylene; Chlorinated hydrocarbons such as chloroform and carbon tetrachloride; Ethers such as dioxane and tetrahydrofuran; Acetone, cyclohexanone,
Ketones such as isophorone; esters such as ethyl acetate, ethylene glycol acetate and dibutyl maleate;
Examples thereof include alcohols such as methanol, n-hexanol, and ethylene glycol; polar solvents such as dimethylformamide and dimethylsulfoxide, and liquid carriers such as water. Further, as the gas carrier, air, carbon dioxide gas, Freon or the like may be used for mixed injection.

In addition, examples of surfactants and dispersants for improving the performance of the present agent such as adhesion to animals and plants, improvement of absorption, dispersion of drug, emulsification, spreading and the like include alcohol sulfates, alkyl sulfonic acid Salt, lignin sulfonate, polyoxyethylene glycol, etc. are used.

Furthermore, in order to improve the properties of the formulation,
For example, carboxymethyl cellulose, polyethylene glycol, gum arabic and the like are used.

The above-mentioned carrier, surfactant, dispersant and auxiliary agent may be used alone or in combination depending on the purpose.

When the compound of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight in the emulsion and 0.3 to 2 in the powder.
5% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, usually 0.5 to 5% by weight for oil formulations, and usually 0.5 to 5% by weight for aerosols.

These preparations are diluted to an appropriate concentration and sprayed on the plant foliage, soil, water surface of paddy fields, or directly applied, and used for various purposes according to their respective purposes.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.
These examples do not limit the scope of the invention in any way. The compound number is the number of the compound shown in Table 1 below.

Example 1 5-Chlor-1,3-dimethyl-pyrazole-4-formaldoxime 0-2- [4- (2-methoxyethyl) phenoxy] ethyl ether 5-chloro-1,3-dimethyl-pyrazole-4 -Formaldoxime 0.9 g and 2- [4- (2-methoxyethyl) phenoxy] ethyl bromide 1.3 g were dissolved in dimethylsulfoxide 30 ml, and then powdered potassium hydroxide 0.4 g was added with stirring at room temperature. The mixture was stirred at room temperature for 5 hours.

After completion of the reaction, water was added and the oily substance separated was extracted with ethyl acetate. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the obtained oily substance was subjected to column chromatography (Wakogel C-200, hetyl acetate: hexane =
(1: 5 elution), 1.5 g of the desired product as a colorless oil.
I got

mp 60-62 ° C. According to the method described in Example 1 above, the compounds shown in Table 1 were produced.

Example 2 5 parts by weight of the compound of Compound No. 2, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoperex powder (trade name; manufactured by Kao Atlas) and 2 parts by weight of sodium lignin sulfonate were uniformly mixed. Then, a small amount of water was added and kneaded, then granulated and dried to obtain granules.

Example 3 10 parts by weight of the compound of mixture No. 4, 70 parts by weight of kaolin,
18 parts by weight of white carbon, 1.5 parts by weight of neoperex powder (trade name; manufactured by Kao Atlas) and 0.5 parts by weight of demol (trade name; manufactured by Kao Atlas) were uniformly mixed and then pulverized to obtain a wettable powder. .

Example 4 20 parts by weight of the compound of Compound No. 4, 70 parts by weight of xylene, and 10 parts by weight of toxanone (trade name; manufactured by Sanyo Chemical Industry Co., Ltd.) were uniformly mixed and dissolved to obtain an emulsion.

Example 5 Efficacy test against diamondback moth The compounds shown in Table 1 were prepared according to Example 3, and cabbage leaf pieces (5 cm x 5 cm) were placed in a chemical solution containing 1000 ppm of water containing a surfactant (0.01%). Soak for 30 seconds and place in a plastic cup. After air-drying, 10 third-instar larvae of Plutella xylostella were released, covered, and allowed to stand in a constant temperature room at 25 ° C. The number of live and dead insects was counted 2 days later, and the death rate was calculated. The results are shown in Table 2.

In Table 2, those with a mortality of 100% are shown as A, those with 99-80% as B, those with 79-60% as C, and those with 59% or less as D.

Example 6 Efficacy test against adult female mites of Tickworm
I tried it. On the other hand, the compounds shown in Table 1 were prepared according to Example 3, and 1000 pp of water containing a surfactant (0.01%) was added.
Leaf pieces were dipped in a chemical solution of m for 10 seconds. After leaving it in a constant temperature room at 25 ° C, the number of live and dead insects was counted 3 days later, and the acaricidal rate was calculated.

Table 3 shows A with a miticidal rate of 100%, 99-80%
B for 79, 60 to 60% for C, and 59% or less for D
Displayed as

Claims (2)

(57) [Claims] (1) General formula [In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, R ² represents an alkyl group having 1 to 5 carbon atoms, n represents 1 to 3, n is 2 or When representing 3, R ² may be the same or different. A represents an alkylene group having 1 to 5 carbon atoms]. 2. An insecticide / acaricide containing the compound of formula (1) according to claim 1 as an active ingredient.