JPH02233679A - Pyrazole compound and insecticide and acaricide containing the same as active ingredients - Google Patents

Abstract

NEW MATERIAL:A pyrazole compound of formula I [R<1> is 1-4C alkyl; R<2> through R<4> are H, 1-4C alkyl; X is H, halogen, 1-4C alkyl, or R<2> and X may incorporate to form group of formulas IV and V (R<5> is H, 1-3C alkyl); Y is O, NH; n is 0, 1, 2]. EXAMPLE:2,3-Dihydro-2,2-dimethyl-7-benzofuranyl-4-chloro-3-ethy-l-1-me thyl-5-py- razole-carboxylate. USE:Insecticide or acaricide having marked activity of controlling insects in Coleoptera, Lepidoptera, Hemiptera, Orthoptera, Diptera or the like and eggs and larvas of mites which are parasitic on plants. PREPARATION:A compound of formula II (Z is Cl, Br, OH, methoxy, ethoxy, propoxy) is allowed to react with a compound of formula III to give the com pound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel pyrazole compound and an insecticide or acaricide containing the same as an active ingredient.

[Conventional technology]

As an example of a compound having a similar structure to the compound of the present invention, one having fungicidal activity is Pest. Bio. Ph
y. , 2j, /63 (/9r&), JP-A-ShojJ-
ryttr publication and JP-A-60-34A Tako-9 K1, and those having herbicidal activity are JP-A-60-34A Tako No. 9 K1.
666j, and those having medicinal activity are disclosed in JP-A No. 7-6269 and JP-A-4! ．． r-yo667l publication, Japanese Patent Publication No. Sho jJ-43r Ko No. 0, Japanese Patent Publication No. Sho ZS-
<Zμ711 publication, Japanese Patent Application Laid-open No. Shojt-7307/publication,
Tokukai Akira! Tatata No. 272 and J. Pharm.
Sci. , 7 Hiro, 1013 (ltarrz), but there are no reports on insecticidal or acaricidal activity.

On the other hand, FarmacO*Ed. Sci. , ko2, t92
(/ta67) contains N-penzyl-3-methyl-virazolecarpoxamide and 3-methyl-j-virazolecarboxylic acid pendyl ester in the t-th order, Rev. R
oum. Chim. , JJ, /jllc/971r
) is N-benzyru/-(2,μ-dinitrophenyl)-3-biphenyl-y-virazolecarboxamide, and JP-A-Sho-Zrort No. K is
-(4'-Hydroxybenzyl)-1,3-dimethyl-! -virazolecarbogisamide and N-(4!-hydroxycarbonylmethoxybenzyl)-/,J-dimethyl-3-virazolecarboxamide have been described, but the presence or absence of insecticidal and acaricidal activity of these compounds is unknown. There are no reports.

Moreover, the above-mentioned publications and literature do not describe any compounds having a penzofuran ring.

[Problem that the invention seeks to solve]

In recent years, long-term use of insecticides has caused insects to become resistant.
Control using conventional insecticides has become difficult. For example, a wide range of insect pests are resistant to typical insecticides such as organic phosphorus agents and carbamate agents, making it difficult to control them. or. Development of resistance has also been reported against synthetic pyresq-id insecticides, which have attracted attention in recent years. On the other hand, some organic phosphorus agents or carbamate agents are highly toxic, and others disturb the ecosystem due to their persistence, creating an extremely worrying situation. Therefore, it is expected to develop new insecticides that exhibit excellent control effects even against insect pests that are resistant to conventional insecticides, and that have low toxicity and low persistence.

[Means for solving problems]

The inventors of the present invention have conducted extensive studies to address this situation, and as a result, have discovered a novel pyrazole compound having excellent insecticidal and acaricidal activity, and have completed the present invention.

That is, the gist of the present invention is the following general formula (1)? In the above formula, Rl represents a C■ to C4 alkyl group, R2 represents a hydrogen atom or a C, to C, alkyl group, and X represents a hydrogen atom, a halogen atom, or a C1 to C4 alkyl group.
R2 and X are together, R! 1 is hydrogen atom i or C.I. ~C.
represents an alkyl group. ) may be formed. Y represents an oxygen atom or H-1N-, R3 represents a hydrogen atom or an alkyl group of C, ~d, and R4 represents a hydrogen atom or an alkyl group of C, ~C4. n represents 0 and/or . It consists of insecticides and acaricides containing pyrazole compounds represented by

Hereinafter, the present invention will be explained in detail by giving specific examples. In the above general formula (1), Rl is a C1 to C4 straight chain or branched group such as a methyl group, an ethyl group, an n-propyl group, an isobrobyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, etc. Represents a chain alkyl group, R2 is a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-
Represents a 01-C4 straight-chain or branched alkyl group such as a butyl group or a t-butyl group; X is a hydrogen atom; a fluorine atom, a chlorine atom, a bromine atom, etc.; -probyl group, improvir group, n-butyl group,
C such as isobutyl group, sec-butyl group, t-butyl group, etc.
1 to C4 linear or branched alkyl group R2 and X
may be formed. R5 is a hydrogen atom;
C, represents a straight chain or branched alkyl group, H Y represents an oxygen atom or 1N1, R3 and R4 are hydrogen atoms; methyl group, ethyl group, n-probyl group, imbrovir group, ropetyl group, isobutyl group , sec-
It represents a C1 to C4 linear or branched alkyl group such as a butyl group or a t-butyl group, and n represents 0, 1 or co.

Specific examples of the birazole compound represented by the above general formula (1) include the compounds shown below.

CH, CH. CH, CH. one CH, CH, one 〇〇、 Next, the method for producing the compound of the present invention will be described.

The compound of the present invention represented by the general formula (1) can be produced according to the following reaction formula.

♂ CH, (II) CH. [1)? In the formula, R'', R2.R3, R', X, Y and ■
is as defined in the general formula [1) above, and Z represents a chlorine atom, a bromine atom, a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, or the like. ) In the above general formula (II), when Z represents a chlorine atom or a bromine atom, aromatic hydrocarbons such as benzene, toluene or xylene; ketones such as acetone, methyl ethyl ketone or methyl isoptyl ketone; chloroform or Halogenated hydrocarbons such as methylene chloride; Water; Esters such as methyl acetate or ethyl acetate; Tetrahydrofuran,
In a polar solvent such as acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone or dimethylsulfoxide, θ to 30°C, preferably 0-j
The compound of the above general formula (13) can be obtained by reacting the compound of the above general formula [...] with the compound of the above general formula ([[) in the presence of a base with Ic. Examples include sodium oxide, potassium hydroxide, sodium carbonate, potassium carbonate, pyridine, and triethylamine.

In addition, in the above general formula ('), when Z represents a hydroxyl group, methoxy group, ethoxy group or propoxy group, no solvent or a high boiling point solvent such as N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc. medium, ip
The compound of the above general formula [l] can be obtained by reacting the compound of the above general formula and the compound of the above general formula [■] at θ~23-0°C, preferably 00-250°C. .

Incidentally, as a method for synthesizing the compound represented by the above general formula (ill), for example, 2.3-dihydro 2. -2-dimethylpenzofuranol is synthesized by the method described in Japanese Patent Publication No. 1993-13-Taoyu. Furthermore, hydroxymetherpenzofuran can be synthesized by using hydroxybenzoic acid ester as a starting material and sequentially methallyl etherification, thermal transfer, and reduction by a conventional method according to the method described in Japanese Patent Publication No. 13-21176. can.

Furthermore, penzofuranylmethylamine can be easily synthesized by chlorinating this with thionyl chloride or the like in a conventional manner, imidizing it with potassium phthalimide, and decomposing it with hydrazine hydrate.

[For production]

The compound represented by the general formula (1) has remarkable control activity against insects of the following orders Coleoptera, Lepidoptera, Hemiptera, Orthoptera, and Diptera, as well as eggs and larvae of Acari that parasitize plants. Of course, it is not limited to these.

l Hemiptera; planthoppers such as the brown-bottomed planthopper, brown-bottomed planthopper, and brown-bottomed planthopper, leafhopper, . + Leafhoppers such as the giant leafhopper, Aphids such as the Japanese peach 7 Aphids 2 Lepidoptera: Spodoptera: Spodoptera nigra, Aedes aegypti, Culex mosquito, etc. 341r order: Tohiro Aegypti Diptera: Common househopper, Aedes aegypti, Culex mosquito, etc. Spider mites: Two-spotted spider mites When using the compound of the present invention represented by the above general formula (1) as an insecticide or acaricide, it may be used alone, but it is usually used as an auxiliary agent like conventional agricultural chemicals. Formulated into emulsions, powders, wettable powders, liquids, etc., using
Or use it diluted. Examples of auxiliary agents include solid carriers such as those used in the production of insecticides, water, hydrocarbons such as cyclohexane, benzene, xylene, and toluene, halogenated hydrocarbons such as chlorobenzene, ethers, amides such as dimethylformamide, ketones, etc. Examples include solvents such as -yL7 alcohols and nitrites such as acetonitrile, and other surfactants such as known emulsifiers and dispersants.

In addition, other insecticides, acaricides, fungicides,
It can also be mixed or used in combination with insect growth regulating substances, plant growth regulating substances, and the like.

The concentration of the active ingredient in the formulated insecticide and acaricide is not particularly limited, but it is usually 0. j, 20 weight ratio preferably /-/0 weight ratio, hydrating agent 1~TAO weight ratio preferably /0-40 weight ratio, emulsion 1~90 weight ratio preferably 70~UO weight ratio Contains ingredients.

When the compound represented by the above general formula (1) is used as an insecticide, the active ingredient is usually used at a concentration of 1,000 ppm, preferably in the range of /o to tooppm.

〔Example〕

Next, the present invention will be explained in more detail with reference to production examples, formulation examples, and test examples of the compounds of the present invention. The present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 2,J-dihydro 2,2-dimethyl-7-penzofuranyl-Koichi chloro-3-ethyl-1 Preparation of methyl-3-virazolecarboxylate Rubonic acid 8? t and thionyl chloride S2 were heated under reflux for 1 hour. After thionyl chloride was distilled off from the reaction solution under reduced pressure, the residue was dissolved in 30.1 g of toluene.

This 2, J-dihydro-2, Kodimethel-? -Hydroxypenzofuran i. bt Totori: After dropping 20 d of r-telamine into a 20 d solution of toluene at room temperature, 2
The mixture was stirred for an hour, poured into ice water, and extracted with toluene. The toluene layer was washed with an aqueous sodium carbonate solution, water, and saturated brine. After drying over anhydrous sodium sulfate, the residue was concentrated under reduced pressure and subjected to silica gel column chroma. The above target product was purified by chromatography. Got 3P.

'HNMR(CDCI,)δf)I)m: /. 2k
(t, JH)z, *t(st4H) ko, a
y(q.-28)3. os (s.koH)*. z&(s,
jH)? ．． 7 7 ~7.7 (m. .yH)I R
(KBr) crIL-':ko970,/'/170
, /420, /60θ, /'IgO. /da'10, /2
Ku0, /230, //20, //00, ggO, Ku6Q Example No.
Preparation of -penzofuranylmethyl)-q-chloro-3-ethyl/-methyl-5-virazolecarboxamide (compounds &j' in Table I) terchloro-3-ethyl-l-methyl-S-virazolecarboxylic acid o. gt and theonyl chloride 2 were heated under reflux for 1 hour. After thionyl chloride was distilled off from this reaction solution under reduced pressure, the residue was dissolved in toluene. This was converted into co,3-dihydro-2,2-dimethyl-5-
Penzofuranylmethylamine 0.72 and triethylamine 0.72. 0 to s in toluene'IOvtl solution of St.
After the dropwise addition, the mixture was stirred for several hours, poured into ice water, and extracted with toluene. The toluene layer was washed with an aqueous sodium carbonate solution, water, and saturated brine. After drying over anhydrous sodium sulfate, it was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the above-mentioned target product 8Q2.
NMR (CDCIg) δp prn j /
．． -2 3 (t, JH)1.4L J'
(s, 4H) 2. A J (q, 2H)3
．． 02 (s, JH) Hiroshi, / 6 (s, JH
) μ. Evening J- (d, JH) 4.7 / (d
,/H)t,7 ~7.2 1 (m, JH)IR
(KBr)cWy,! 3uO, 2ta7j, .
2ta. 3j, /6171, /j≠0, /Hirota0,1λta0,/2tj,10ta! , j Example 3 Synthesis was carried out according to the method of Example 1 or 2, and the following table 1
The described compound was obtained.

Table 1 Next, formulation examples of the compounds of the present invention are shown. In addition, below, “Part J
, r%J are "parts by weight" and "weight 俤" respectively.
means.

Formulation Example 1: Wettable powder 20 parts of the compound of the present invention from Table 1, Curbrex@10 (
Shionogi Pharmaceutical Co., Ltd., trade name) Ko O part, N, N kaolin clay (Tsuchiya Kaolin Co., Ltd., trade name) J'j part, higher alcohol sulfate ester surfactant Solbol 1070 (Toho Kagaku Co., Ltd., trade name) j part Blend, mix and grind evenly,
An irrigation agent containing UO% of the active ingredient was obtained.

Formulation Example K: Powder Part λ of the compound of the present invention in Table 1, clay (manufactured by Nippon Merck Co., Ltd.)
23 parts and J part of white carbon are uniformly mixed and pulverized,
．． A 2% powder was produced.

Formulation Example 3: Emulsion 20 parts of the compound of the present invention in Table 1 is dissolved in a mixed solvent consisting of 3j parts of xylene and 30 parts of dimethylformamide, and the polyoxyethylene surfactant Solpol 300rXC (Toho Kagaku Co., Ltd., trade name) is added to this. /j parts were added to obtain an emulsion containing 20 parts of the active ingredient.

Formulation example μ: Floor pull agent 30 parts of the compound of the present invention shown in Table 1, j parts of ethylene glycol previously mixed, j parts of Solbol 80 JO32 (Toho Chemical Co., Ltd., trade name), 0.0 parts of xanthan gum. / part was well mixed and dispersed in 74.2 parts of water. Next, this slurry-like mixture was wet-milled using a Dyno Mill (Ci/Mul Enterprises) to obtain a stable floor pull agent containing 30 parts of the active ingredient.

Test Example 1: Effect on adult red spider mites 10 heads of female adult red spider mites are released onto the leaf disc (diameter 2 cm) of kidney bean leaves. This is a solution in which the compound of the present invention prepared according to the method of Formulation Example 1 is diluted with water to a predetermined concentration!
We were sprayed using a rotary spray tower (manufactured by Mizuho Rika).

(1 concentration, 2 repetitions.) After treatment 2≠ hours, the survival or death of the adults was investigated, and the acaricidal rate (correspondence) was determined. The results are shown in Table 2.

Test Example λ Effect on Namino mite eggs on leaf discs (diameter 2 cm) of green bean leaves! Release the female adult mites on the head. Eggs were allowed to lay on the leaf disc for 2θ hours after release, and then the female adults were removed. This was sprayed with j ml of a solution prepared by diluting the compound of the present invention prepared according to the method of Formulation Example 1 with water to a predetermined concentration using a rotary spray tower (manufactured by Mizuho Rika). (L concentration, 2 repetitions.) After j days of treatment, the number of unhatched eggs and the number of hatched larvae were investigated, and the ovicidal rate (%) was determined. The results are shown in Table 2.

Test Example 3 Effect on brown planthopper larvae Budding rice seedlings are set in a glass cylinder (diameter: 3 cWI, length: 7 cm), and j heads of brown planthopper q-instar larvae are released.

To this was added a solution of 0.0% of the compound of the present invention prepared according to the recipe of Formulation Example 3 diluted with water. j. 1 was sprayed using a spray tower (manufactured by Mizuho Rika). (1 concentration, ≠ repetition.) After 2≠ days of treatment, the survival of the larvae was investigated, and the insecticidal rate (%) was determined. The results are shown in Table 3.

Test Example μ Effect on diamondback moth larvae Cut cabbage leaves (j x s cm ) were immersed for 1 minute in a solution prepared by diluting the compound of the present invention with water, prepared according to the method of Formulation Example 1. After soaking, the mixture was air-dried and placed in a plastic cup (7 m in diameter), into which J third instar larvae of the diamondback moth were released (1 concentration, 2 replicates).

Two days after the insect release, the larvae were checked to see if they were alive or dead, and the insecticidal rate was determined. The results are shown in Table 3.

Table 3 [Effects of the Invention] As is clear from the above examples, the compounds of the present invention have excellent insecticidal and acaricidal effects.

Claims (2)

[Claims] (1) The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼…[I] (In the above formula, R^1 represents an alkyl group of C_1 to C_4, and R^2 is a hydrogen atom or a C_1 to C_4 represents an alkyl group, and X is a hydrogen atom, a halogen atom, or C_1~
C_4 represents an alkyl group, and R^2 and (representing an atom or an alkyl group of C_1 to C_2) may be formed. Y is an oxygen atom or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^3 is a hydrogen atom or C_1
~C_4 represents an alkyl group, and R^4 represents a hydrogen atom or a C_1 to C_4 alkyl group. n represents 0, 1 or 2. ) Pyrazole compound represented by (2) An insecticide or acaricide containing the pyrazole compound according to claim (1) as an active ingredient.