JPH0253704A - Trialkylsilylpyrazoles and insecticidal and miticidal agent containing same compound as active component - Google Patents

Abstract

NEW MATERIAL:The pyrazoles of formula I (R<1> is methyl or ethyl; X is halogen, methyl or ethyl; R<2>-R<4> are independently methyl or ethyl). EXAMPLE:A compound of formula I wherein R<1> is methyl, X is fluorine and R<2>, R<3> and R<4> are methyl. USE:An insecticidal miticide having excellent insecticidal and miticidal effect. PREPARATION:The compound of formula I can be produced e.g., by reacting a compound of formula II (Z is Cl, Br, OH, methoxy, ethoxy or propoxy) with a compound of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to novel pyrazoles and insecticides, acaricides, and agents for killing mites parasitic on animals that contain the same as an active ingredient.

[Problems to be solved by conventional technology and invention]

Among the compounds having a similar structure to the compounds of the present invention, those having bactericidal activity are Pe5t and Bio.

Phy, +2! ;, /Otsu 3 (/9g&), Tokukai Sho 3
2-gqitg publication and JP-A-ShoA O-, 74 (9
In Publication No. 19, there is also a substance with herbicidal activity published in JP-A-Sho! ;
7-10AAI,! In Japanese Patent Publication No. R, Akihiro 7-626, which has medicinal activity, Publication No. 11g-!
;41,7/ Publication, Japanese Patent Application Publication No. 32-gJg'IO, Japanese Patent Publication No. 3S-99757, Japanese Patent Application Publication No. 3S-99757, Publication No. 5t-7,3
07/No. Publication, JP-A-Sho,! T? -9! ;27 Publication and J, Pharm, Sci, ? i, 10/JC
/ 9g! ;), but there are no reports on insecticidal or acaricidal activity. Further, in the above-mentioned publications and literatures, there is no mention of an aralkyl group as a substituent for the amine moiety.

On the other hand, Farmaco, Ed, 5ci-e 22.
t92 (/917) KU, N-benzyl-3i
Methyl-5-pyrazolecarboxamide and 3-methyl-S-pyrazolecarboxylic acid pendyl ester, Rev, Roum, Chim, +2. ,? +
/ Left side / (/97g) contains N-benzyl-
/-(2,Q-dinitrophenyl-3-biphenyl-
5-pyrazole carboxamide is still in Japanese patent publication! ; 0
−! rl! :0! In the rA publication, N-(Q-hydroxybenzyl)-/,? -dimethyl-5-pyrazolecarboxamide and N-(couhydroxycarbonylmethoxybenzyl)-i,,y-dimethyl-3-pyrazolecarboxamide have been described, but there have been no reports on whether or not these compounds have insecticidal or acaricidal activity. do not have.

Further, there have been no reports on carboxamides in which the amine moiety is trialkylsilylbenzylamine.

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 have become resistant to organophosphorous 5-carbamate agents, which are typical insecticides, making it difficult to control them. In addition, insect pests that have developed resistance to synthetic pyrethroid insecticides, which have attracted attention in recent years, have been reported.

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, the development of 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 are expected.

[Means for solving problems]

In view of the above problems, the present inventors conducted extensive research, and as a result, discovered a novel pyrazole derivative having excellent insecticidal and acaricidal activity, and completed the present invention.

That is, the gist of the present invention resides in pyrazoles represented by the following general formula CI) and insecticides and acaricides containing the same as an active ingredient.

(In the above formula, R1 represents a methyl group or an ethyl group, X represents a halogen atom, a methyl group, or an ethyl group, R2, R
3 and independently represent a methyl group or an ethyl group. ) Hereinafter, the present invention will be explained in detail. In the general formula (I), R' represents a methyl group or an ethyl group, and X represents a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; It is. R2, R3 and W each independently represent a methyl group or an ethyl group, preferably R2, R3 and all are methyl groups. Specific examples include, but are not limited to, the compounds listed in Table 1.

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

(II) (I) (In the above reaction formula, R1, R2, R3, R4 and X are as defined in the above general formula CI), and Z is a chlorine atom, a bromine atom, a hydroxyl group, a methoxy group, an ethoxy group Or represents a propoxy group. ) In the above general formula (n), when Z represents a chlorine atom or a bromine atom, an aromatic hydrocarbon such as benzene, toluene or xylene; ketones such as acetone, methyl ethyl ketone or methyl isobutyl keto/etc.; chloroform or chloride; In halogenated hydrocarbons such as methylene; water; esters such as methyl acetate or ethyl acetate; aprotic polar solvents such as tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone or dimethylsulfoxide; The compound of the above general formula CI) can be obtained by reacting the general formula (III) in the presence of a base at -30°C, preferably o -t 'C. Examples of the base include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, pyridine, and triethylamine.

In general formula (n), when Z represents a hydroxyl group, a methoxy group, an ethoxy group, or a propoxy group, it may be used without a solvent or in a high boiling point solvent such as N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc. , 13θ
The compound of the above general formula (I) can be obtained by reacting the compound of the general formula (III) at ˜Sθ°C, preferably 0°C.

In addition, the compound represented by the above general formula (n) is, for example, Bu
l 1. It can be produced according to the method described in Soc, Chim, France+Chim (19/, A).

[For production]

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

7 Hemiptera: Planthoppers such as the brown planthopper, brown planthopper, and brown planthopper, leafhoppers such as the black leafhopper and giant leafhopper, and aphids such as the green peach aphid. Orders: House fly, Culex pipiens, Culex mosquito, etc. 5 Spider mites: Two-spotted spider mite, false red spider mite, Citrus spider mite, etc. 6 Ixodes: Animal parasitic mites such as Ixodes spp. When used, they may be used alone, but they are usually prepared in the form of emulsions, powders, irrigation agents, solutions, etc. using adjuvants like conventional agricultural chemicals, and used as they are or diluted. As adjuvants, those commonly used in insecticide formulations can be used. For example, talc,
Solid carriers such as kaolin, diatomaceous earth, clay, and starch, water, hydrocarbons such as cyclohexane, benzene, xylene, and toluene, halogenated hydrocarbons such as chlorobenzene, ethers, amides such as dimethylformamide, ketones, Examples include solvents such as alcohols and nitriles such as acetonitrile, and 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 is usually O,S-20% by weight for powders, preferably 7 to IO% by weight, and /-? for irrigation agents. 0 weight ratio, preferably 70-g.

% by weight, the emulsion is /-90% by weight, preferably 10-yoM
Contains active ingredients of fitiy.

When the compound represented by the above general formula (I) is used as an insecticide, the active ingredient is usually ! -1000 ppm, preferably in the concentration range of /0 to 500 ppm.

〔Example〕

Hereinafter, the present invention will be specifically explained using production examples, formulation examples, and test examples of the compounds of the present invention, but the present invention is not limited to the following examples unless the gist thereof is exceeded.

Production Example N-(4'-)limethylsilylpenzyl]-trichloro-3-ethyl-7-methyl-terhirazolecarboxamide Production of chloro-3-ethyl/-methyl-terpyrazolecarboxylic acid/, g 9? and thionyl chloride 6θ2 were heated under reflux for 1 hour. After thionyl chloride was distilled off under reduced pressure, the residue was dissolved in 10 ml of toluene. Add this to 20ml of a toluene solution of cootrimethylsilylbenzylamine/7de2.
O~i inside.

It was added dropwise at ℃. After the dropwise addition, the mixture was stirred for 2 hours, poured into ice water, and extracted with toluene. Add toluene layer to sodium carbonate aqueous solution,
Washed with water and saturated saline.

After drying over anhydrous sodium sulfate, it was concentrated under reduced pressure.

The residue was purified by silica gel column chromatography.
Compounds listed in Table-7 ()ffi/g) J,/
, 5-9, n2; /,! rJA7 was obtained.

The NMR and IR spectra of the obtained compound are shown below.

'HI'MFL(CC1,,)δppm; o, ko5
(S, deH) /,2(t,,)H)uJl(q,2
H) K, 0j (s,,?H) 11.5 (d, koH)
Otsu, 9(b, /H)7.23Cd,2H)7. ri5(d
,, 2H) IR (CTL-Re; 3/7.ao, aqs
o,/Otsu60. /jJ! ;/! ;J3. / +2'
Examples of formulations of the compounds of the present invention are shown below. In addition, below, "part J, r% J" means
They mean "parts by weight" and "parts by weight," respectively.

Formulation example/ 20 parts of the compound of Preparation Example, Carplex #g.

(Shionogi Pharmaceutical Co., Ltd., trade name) 20 parts, N, N kaolin clay (Ueya Kaolin Co., Ltd., trade name) SS part, higher alcohol sulfate ester surfactant Tsurupol go 7o (Toho Kagaku Co., Ltd., trade name) 5 parts were mixed and pulverized uniformly to obtain an aquarium containing 0% of active ingredients.

Formulation Example λ 2 parts of the compound of the present invention in Production Example, 93 parts of clay (Nihon Ri/'1 Co., Ltd.), and 5 parts of white carbon were uniformly mixed and pulverized to produce 2 powders.

Formulation Example 3 20 parts of the compound of the present invention in Production Example was dissolved in a mixed solvent consisting of 33 parts of xylene and 30 parts of dimethylformamide, and the polyoxyethylene surfactant Tsurupol 3oosx (Toho Kagaku Co., Ltd., trade name) 75 was added to this. In addition,
An emulsion containing an active ingredient, 2θ modulus, was obtained.

Formulation Example: 30 parts of the compound of the manufacturing example, g parts of ethylene glycol previously mixed, 5 parts of Tsurpol AC, 703, z (Toho Fhi Gakusha, trade name), o and i parts of xanthan gum, water sb and q. The mixture was well mixed and dispersed. Next, this slurry-like mixture was wet-milled using a Dyno Mill (Shinmaru Entergrise Co., Ltd.) to obtain a stable flowable agent containing 30% of the active ingredient.

Test Example 1 Effect on adult two-spotted spider mites Ten female adult two-spotted spider mites are placed on a leaf disk (diameter 2 cm) of a kidney bean leaf. To this was added Sml of a saliva solution prepared by diluting the compound of the present invention prepared according to the procedure of Formulation Example 1 with water to a predetermined concentration.
Spraying was performed using a rotary spraying tower (manufactured by Mizuha Rika).

(Concentration, repetition.) After 2 q hours of treatment, the survival of the adults was investigated, and the acaricidal rate (%) was determined.
) was sought. The results are shown in Table 1.

Test Example Effect on eggs of two-spotted spider mite Five adult female two-spotted spider mites are placed on a leaf disc (diameter, 2c!rL) of a kidney bean leaf. Eggs were allowed to lay on leaf discs for 20 hours after adulthood, and then the female adults were removed. To this, 5 ml of a saliva solution of the compound of the present invention prepared according to the procedure in Formulation Example 1 diluted with water to a predetermined concentration was sprayed using a rotary spray tower (manufactured by Mizuha Rika). (1 concentration, 3 repetitions.) Five days after the 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 1.

Test Example 3 Effect on brown planthopper larvae Seed budding rice seedlings into a glass cylinder (diameter 3 crn, length/7 degrees), and collect 5 adult brown planthopper instar larvae. to this,
A solution o, sml of the compound of the present invention prepared according to the procedure in Formulation Example 3 diluted with water was sprayed using a scattering tower (manufactured by Mizuha Rika). (1 concentration was repeated.) 29 hours after treatment. , investigate whether the larvae are alive or dead, and determine the insect killing rate (忤)
I asked for The results are shown in Table-3.

Test Example G: Effect on diamondback moth larvae Cut cabbage leaves (!×Scr/L) were immersed in a solution prepared by diluting the compound of the present invention prepared according to the treatment in Formulation Example 1 with water for 7 minutes. After soaking, air dry and use a plastic cup (diameter 7
crn), and five adult diamondback moth 3rd instar larvae were placed therein. (Concentration: 1, repeat.) Two days after the adult larvae, the survival or death of the larvae was investigated, and the insecticidal rate (chi) was determined. The results are shown in the table.

Table 2 Table 3 Table [Effects of the Invention] The pyrazoles of the present invention have excellent insecticidal and acaricidal effects and are of high value.

Claims (3)

[Claims] (1) Pyrazole represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I) (In the above formula, R^1 represents a methyl group or an ether group, and
represents a halogen atom, methyl group or ethyl group, R^2
, R^3 and R^4 each independently represent a methyl group or an ethyl group. ) (2) X is a chlorine atom or a bromine atom, R^2, R^
The pyrazole according to claim 1, wherein 3 and R^4 are all methyl groups. (3) An insecticide or acaricide containing the pyrazole according to claim 1 as an active ingredient.