JPS61148168A - Production of benzimidazole derivative - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful as an insecticide, by reacting an aniline derivative with a carboxylic acid or its reactive derivative. CONSTITUTION:A compound shown by the formula I (R2 and R3 are H, halogen, nitro, alkyl, alkenyl, cycloalkyl, alkylsulfonyl, etc., or R2 and R3 are bonded to form ring; X is O, S, methylene, sulfonyl, etc.) is reacted with a compound shown by the formula II (R1 is H, or lower alkyl) or its reactive derivative in a molar ratio of 1:1-10 at 50 deg.C- the boiling point of the reaction mixture for 1-50hr, to give a compound shown by the formula III. The reaction may be carried out in an inert solvent such as water, benzene, CCl4, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to compounds of the general formula (I) [wherein R1 represents a hydrogen atom or a lower alkyl group, R2 and R3 are the same or different, and a hydrogen atom, a halogen atom, a nitro group, Cyano group or optionally substituted lower alkyl group, lower alkenyl group, lower alkynyl group, lower cycloalkyl group, lower alkoxy group, lower alkenyloxy group, lower alkynyloxy group, lower cycloalkoxy group, lower alkylthio group, a lower alkenylthio group, a lower anolekynylthio group, a lower cycloalkylthio group, a lower dialkylamino group, a lower alkylsulfonyl group, or a lower alkylsulfinyl group; an optionally substituted saturated or unsaturated 5 atom containing 0 to 2 atoms or sulfur atoms in the ring
It can form a membered ring or a six-membered ring. X represents an oxygen atom, a sulfur atom, a methylene group, a sulfonyl group, a sulfinyl group or an imino group. ] It is related with the manufacturing method of the benzimidazole derivative shown by these.

That is, the present invention is based on the general formula [■] 9 [wherein RweRs and X have the same meanings as above. ] An aniline derivative represented by the general formula (I[[) [wherein,
R1 has the same meaning as above. This is a method for producing a benzimidazole derivative represented by the general formula (I), which is characterized by reacting a carboxylic acid represented by the formula (I) or a reactive derivative thereof.

Certain benzimidazole derivatives, such as 1-(8
, 7-dimethylocta2.6-cyenyl) penzimitasol has insecticidal efficacy against house flies and the like, according to Agric.

Biol, Chem, 46(6) 1715(1
982). However, these compounds cannot necessarily be said to be sufficient as active ingredients for insecticides.

The compounds of the present invention have excellent insecticidal efficacy against Diptera pests such as Culex Culex and Culex aegypti. In addition, it has excellent acaricidal efficacy against spider mites such as false red spider mite and orange 11 mite, and is also highly effective against spider mites that have developed resistance to existing acaricides. It can be used as an active ingredient in insecticides, acaricides, epidemic prevention insecticides, etc.

An object of the present invention is to provide a method for producing such useful compounds.

Hereinafter, the method for producing the benzimidazole derivative of the present invention will be described in detail.

In the present invention, an aniline derivative represented by the general formula [■] and a carboxylic acid represented by the general formula (III) or a reactive derivative thereof, such as a carboxylic acid anhydride, a carboxylic acid orthoester, a carboxylic acid halide, a carboxylic acid ester , imino acid ester, etc., in the presence or absence of an inert solvent at a temperature of 25 to 200°C, preferably 50°C to the boiling point of the reaction mixture, for 1 to 50 hours.

Suitable inert solvents include water, benzene, toluene,
Examples include carbon tetrachloride, chloroform, ethylene chloride, etc., or mixtures thereof.

Further, the molar ratio of the carboxylic acid represented by the general formula (III) or the reactive derivative to the aniline derivative represented by the general formula [■] is 1:1 to 100. Preferably 1:1~
It is 10.

The aniline derivative represented by the general formula (n) can be produced, for example, by the reaction route shown below.

(If) Mass [■] [In the above formula, R, R, and X represent the same meanings as above, and Y represents a halogen atom. ] A nitrobenzene derivative represented by the general formula 1) and the general formula [
The reaction with the benzylamine derivative represented by [Ma] may be carried out in the presence or absence of an inert organic solvent, and suitable solvents include benzene, toluene, xylene, O-dichlorobenzene, dimethylformamide. ,
Examples include dimethyl sulfoxide. A deoxidizing agent can also be present in the system to promote the reaction.
Preferred deoxidizers include organic bases such as triethylamine and pyridine, and inorganic bases such as potassium carbonate and sodium carbonate.

The reaction temperature ranges from room temperature to the boiling point of the reaction mixture, preferably 10G-200C.

In the nitrobenzene derivative represented by the general formula (ff), the halogen atom represented by Y is a fluorine, chlorine, bromine, or iodine atom, preferably a fluorine atom, a chlorine atom, and a bromine atom.

The molar ratio of the benzylamine derivative represented by the general formula [ma] to the nitrobenzene derivative represented by the general formula (ff) is i:o, s~20, preferably 1:1~8.

Various methods can be used in the reduction step for forming the aniline derivative represented by the general formula [■] from the nitrobenzene derivative represented by the general formula (V [)].

As a reducing agent under acidic conditions, for example, iron can be used. In addition, zinc, tin, tin chloride (■), etc. can also be used as reducing agents. The solvent used in the reaction generally includes hydrochloric acid, acetic acid, etc., the reaction temperature is preferably from room temperature to the boiling point of the reaction mixture, and the reducing agent is usually preferably used in an equivalent amount or more. Using zinc dust as a reducing agent,
If the reaction is carried out, it can be carried out under neutral or alkaline conditions. These methods are described in the literature (Can, J. Che
m,, 88 *2526 (1'960) or J,
Aniline derivatives can be produced by a reaction procedure similar to that of Chem, Soc, *1960 e1187).

In addition, sodium sulfide (Na, S eNa
lS2, Na, 34), sodium hydrosulfide (N
a5H).

Sulfur-based compounds such as sodium dithionite (Na, 5ho4) and ammonium sulfide ((NH4)tS) can also be used. Examples of the solvent used in this reaction include water, aqueous ammonia, alcoholic solvents such as methanol and ethanol, hydrocarbon solvents such as benzene and toluene, and mixed solvents of two or more thereof. The reaction temperature is preferably from room temperature to the boiling point of the reaction mixture, and the reaction is completed in 1 to 50 hours.

Furthermore, the aniline derivative represented by the general formula (n) can also be produced by a catalytic reduction method using platinum oxide, Raney nickel, or the like. For example, when platinum oxide is used as a catalyst, examples of the solvent include ethanol, methanol, ethyl acetate, and water. It is also effective to promote the reaction by coexisting acetic acid, hydrochloric acid, etc. in the system. Generally, the reaction temperature is from room temperature to 110°C, and the pressure can be from atmospheric pressure to 50 atm.

It is necessary to use various methods for these reduction reactions depending on the changes in the substituents R1 and R3 in the nitrobenzene derivative represented by the general formula (Vl). For example, when R3 and R, 8.4- In the case of a nitrobenzene derivative containing a methylenedioxy group, it is necessary to use a reducing agent such as sodium sulfide or platinum oxide, and to use a method that does not contain acidic compounds in the system (also, general formula 11) The nitrobenzene derivative represented by can also be produced by the following reaction.

& [■] 4 [In the above formula, R2, R, Yaku and X have the same meanings as above, and 2 represents a halogen atom. ] The reaction between 0-nitroaniline and the benzyl halide derivative represented by the general formula [■] is generally carried out in an inert organic solvent in the presence of a deoxidizing agent. Preferred deoxidizing agents include organic bases such as triethylamine and pyridine;
Examples include inorganic bases such as potassium carbonate and sodium carbonate, and examples of suitable inert organic solvents include benzene, toluene, xylene, 0-dichlorobenzene, dimethylformamide, and dimethylsulfoxide. The reaction temperature is -50°-250°C, preferably 100°-200°C.

The molar ratio of the benzyl halide derivative represented by the general formula [■] to O-nitroaniline is i:o, s~2, preferably 1:0.8~1.2.

In the benzyl halide derivative represented by the general formula [■], the halogen atom represented by Z represents a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom or a bromine atom.

Further, in the step of reducing the nitrobenzene derivative represented by the general formula [■], when a carboxylic acid represented by the general formula (III) or the reactive derivative thereof is used as a solvent, the general formula (II) is used as an intermediate. It is also possible to obtain a benzimidazole derivative represented by the general formula (I) corresponding to R1 of the carboxylic acid used as a solvent or the reactive derivative without isolating the aniline derivative represented by.

The benzimidazole derivative represented by general formula (I) is
Although it can be manufactured by the method described above, it can also be manufactured by the following method.

[■RI R3 (I) R8 [In the above formula, R4e R1*RI and X represent the same meanings as above. ] This reaction can be promoted by allowing an acid catalyst to coexist in the system. In this production method, the reaction is preferably carried out in the presence of an inert organic solvent. Suitable solvents include benzene, toluene, xylene, O-dichlorobenzene, chloroform, carbon tetrachloride, and the like. Further, the general formula (1) corresponding to R1 of the anilide derivative represented by the general formula [■] % formula % () [wherein R1 represents the same meaning as above. ] can also be used as a solvent, in which case it can also serve as an acid catalyst.

Suitable acid catalysts include sulfuric acid, I)-)reninsulfonic acid, benzenesulfonic acid (CF), and carboxylic acids represented by the corresponding general formula (1) above. The reaction temperature ranges from room temperature to the boiling point of the reaction mixture, and it is also effective to promote the reaction by separating and removing water produced from the reaction system. The reaction is generally 1~
Completed in 50 hours. j General formula [■
The anilide compound represented by can be produced, for example, by the reaction route shown below.

[■]

[In the above formula, R,, R,, R, O, ihiX4tM have the same meanings. ] This reaction is generally carried out in the presence of an inert organic solvent. Suitable inert organic solvents include benzene, toluene, O-dichlorobenzene, chloroform, carbon tetrachloride, and the like. The reaction can be completed by, for example, azeotropically dehydrating water from the reaction system, and a catalytic amount of acids such as benzenesulfonic acid and p-)reninsulfonic acid may also be present. can. The reaction is generally carried out at a temperature range from room temperature to the reaction mixture, and the molar ratio of the aldehyde compound represented by the general formula (II) to the aniline derivative represented by the general formula [■] is from 1:0.5 to 2, preferably 1:0.9-1
．． It is 1.

From the imine compound represented by the general formula (I) to the imine compound represented by the general formula (I)
Various methods can be used in the reduction step for forming the anilide compound represented by I'). Examples include methods using metal hydrogen complex compounds such as sodium borohydride and sodium cyanoborohydride, and catalytic hydrogenation methods using catalysts such as platinum oxide and Raney nickel.

When a metal hydrogen complex compound is used, the reaction is preferably carried out in the presence of an inert organic solvent, and suitable inert organic solvents include methanol, ethanol, tetrahydrofuran, and diethyl ether particles. The reaction can also be promoted by adding hydrogen chloride or the like into the reaction system and carrying out the reaction under acidic conditions. Generally the reaction is 0℃
to the boiling point of the reaction mixture.

When using the catalytic hydrogenation method, the reaction is preferably carried out in the presence of an inert organic solvent, and suitable inert organic solvents include methanol, ethanol, ethyl acetate and the like. The reaction can also be accelerated by adding acetic acid, hydrochloric acid, etc. to the reaction system and carrying out the reaction under acidic conditions. Generally, the reaction ranges from room temperature to the boiling point of the reaction mixture, and the pressure ranges from atmospheric to 50 atmospheres.

Further, when a carboxylic acid represented by general formula (III) or the reactive derivative thereof is used as a solvent in the step of reducing the imine compound represented by general formula (1),
The benzimidazole derivative represented by the general formula CI) corresponding to R1 of the carboxylic acid or the reactive derivative used as a solvent without isolating the anilide compound represented by the general formula [■'] produced as an intermediate. It can also be done with respect.

The anilide compound represented by the general formula [■I] is
The aniline derivative represented by the general formula [■] and the general formula (II
It can also be produced as a reaction intermediate during the reaction with the carboxylic acid represented by I) or its reactive derivative.

(2)- [In the above formula, R,, R,, R, O, iHx represent the same meanings as above, and L represents a leaving group. ] In this reaction, the imine compound represented by the general formula (II') is heated in the presence of an acid catalyst such as hydrochloric acid or sulfuric acid, preferably 10G-200
This is done by heating to ℃. Further, this reaction can be carried out either in the presence or absence of an inert organic solvent, and examples of suitable solvents include benzene, toluene, xylene, and O-dichlorobenzene.

Examples of the leaving group represented by 4 for L in the general formula [1] include a lower alkoxyl group and an amino group.

The imino compound represented by the general formula (II'') can be obtained, for example, by the following reaction.

[In the above formula, R□* R1e Rs and X have the same meanings as above, and R1 represents a lower alkyl group. ] Furthermore, in the above reaction, the imino compound represented by the general formula [■] can be led to the benzimidazole derivative represented by the general formula CI) without isolating it.

The compounds of the present invention and intermediates obtained by the above production method can be processed by column chromatography, distillation,
It can be purified by means such as recrystallization.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Reference Examples.

Example 1 Production of compound (18) A mixture of 2.90 f of N-(4-phenoxybenzyl)-〇-phenylenediamine and 10++ g of acetic acid was heated to reflux with stirring for 6 hours, cooled to room temperature, and then heated under reduced pressure. Excess acetic acid was distilled off. A 5% aqueous sodium hydroxide solution 50-j was added to the obtained oil, and the mixture was extracted with 100 ml of toluene. After washing with water, drying with anhydrous sodium sulfate, distilling off toluene under reduced pressure, and subjecting to silica gel column chromatography, white crystals (mp 145C) of 2-methyl-1-(4-phenoxybenzyl)benzimidazole 2 I got .75 f.

Example 2 Preparation of compound (81) N-(4-(4-ethoxyphenoxy)benzyl)-〇-7enylenediamine 8.841 and ethyl orthoacetate 1
The mixture was heated under reflux for 5 hours with stirring, and after cooling to room temperature, excess ethyl orthoacetate was distilled off under reduced pressure. 6% sodium hydroxide aqueous solution 50% to the obtained oil
ml was added and extracted with 100 d of toluene. After washing with water, drying with anhydrous sodium sulfate, distilling off toluene under reduced pressure, and subjecting to silica gel column chromatography, a colorless liquid (nD 1.598G) of 1-[4-(4-ethoxyphenoxy)benzyl co- 8.15f of 2-methylbenzimidazole was obtained.

Reference Example 1 Production of compound (81) Φ N-(4-(4-ethoxyphenoxy)benzyl)
-〇-7 Preparation of enylenediamine 2-(4-(4-Ethoxyphenoxy)benzylaminoconitrobenzene 8.64f, platinum oxide 0.8Of and ethyl acetate 100d are mixed with hydrogen under stirring). 4゜When hydrogen no longer absorbs sulfur, the reaction system is replaced with nitrogen, and the reaction mixture is passed through the mouth.
After removing the platinum oxide catalyst, the solvent was distilled off under reduced pressure.

The obtained oil was recrystallized from a mixed solvent of benzene and hexane to give white crystals (mp 87.6°C) of N-(4-(4-ethoxyphenoxy)benzyl)-0-phenylenediamine 8. Obtained .01F.

■ Production of 1-(4-(4-ethoxyphenoxy)benzylco-2-methylbenzimidazole) N-(4-(4-ethoxyphenoxy)benzyl]-〇-7enylenediamine 1 obtained in ■
．． The target compound (81
) 1.59F was obtained.

Reference Example 2 Production of Compound (1) ■ Production of 2-(4-phenoxybenzylamino)nitrobenzene A mixture of 15.76r of 0-nitrochlorobenzene and 48.842r of 4-phenoxybenzylamine was mixed with 140-
The mixture was heated and stirred at 150°C for 6 hours. After cooling to room temperature, 200 st of toluene was added, and the mixture was washed with 600 ml of 5% hydrochloric acid aqueous solution in 8 portions, washed with water, dried over anhydrous sulfuric acid 1-+7 um, and the toluene was distilled off under reduced pressure to obtain a yellow color. A crude crystal of was obtained. By recrystallizing from a mixed solvent of toluene and hexane, 20.68f of 2-(4-phenoxybenzylamino)nitrobenzene was obtained as yellow crystals (mp, 88.6°C).

(2) Production of N-(4-phenoxybenzyl)-0-phenylenediamine 8.20f of 2-(4-7 enoxybenzylamino)nitrobenzene obtained in (2).

Hydrogen gas was added to a mixture of 0.80 f of platinum oxide and 100 g of ethyl acetate while stirring. At the point when hydrogen no longer absorbs gas, the reaction system is replaced with nitrogen gas, the reaction mixture is passed through the mouth, the platinum oxide catalyst is removed, and the solvent is distilled off under reduced pressure to form silica gel. N-(4-
phenoxybenzyl)-0-phenylenediamine 2.6
Obtained Tf.

■ Production of 1-(4-phenoxybenzyl)benzimidazole 1.451 of N-(4-phenoxybenzyl)-〇-phenylenediamine obtained in ■ and 5 of formic acid.
The mixture with d was heated to reflux for 6 hours with stirring, and after cooling to room temperature, excess formic acid was distilled off under reduced pressure. 50 ml of 5% aqueous sodium hydroxide solution was added to the obtained oil, and the mixture was extracted with 100 ml of toluene.

After washing with water, drying with anhydrous sodium sulfate, distilling off toluene under reduced pressure, and subjecting to silica gel column chromatography, white crystals (m991°C) of compound (1) 1.81
I got r.

Reference Example 8 Production of compound (31) ■ Production of 2-(4-(4-ethoxyphenoxy)benzylaminoconitrobenzene) 0-Nitroaniline 1.8
8f,N,N-dimethylaniline 1.88? , 4-C4
A mixture of 8.07 F of -ethoxyphenoxy)benzyl bromide and 5 od of xylene was heated under reflux for 6 hours with stirring, and after cooling to room temperature, 100 lIl of water was added and extracted with 100 tel of toluene. After washing with water, drying with anhydrous sodium sulfate, toluene and xylene were distilled off under reduced pressure, and the 2-(4-C4-ethoxyphenoxy)benzylamino Conitrobenzene 2.15
I got an F.

■ Production of 1-(4-(4-ethoxyphenoxy)benzyl-2-methylbenzimidazole) 2-(4-(4-ethoxyphenoxy)benzylaminoconitrobenzene obtained in step 2.1)
Using FM, the same reaction operation as in Reference Example 1 (2) was carried out to obtain white crystals of N-(4-(4-ethoxyphenoxy)benzyl)-〇-phenylenediamine 1.77F, and then this and acetic acid were mixed. The target compound, compound (81) 1.69 F, was obtained by carrying out the same reaction procedure as in Example 1 using 5d.

Reference Example 4 Production of compound (81) N-acetyl-N'-(4-(4-ethoxyphenoxy)benzyl)-〇-7enylenediamine 8.'16f,
p-) Reninsulfonic acid 0.20F# and toluene Bo
The mixture of wl was heated to reflux with stirring and Dean-5ta
The water produced in the rk trap was removed, and the reaction was continued until water was no longer produced, then cooled to room temperature, washed with a saturated aqueous sodium carbonate solution, washed with water, and then the toluene was distilled off under reduced pressure, and the silica gel column was removed. Chromatograph 6J Eini attached, colorless liquid (nD 1.5986) 1-(
8.4Of of 4-(4-ethoxyphenoxy)benzyl-2-methylbenzimidazole was obtained.

Reference Example 6 Production of compound (81) ■ Production of N-acetyl-N'-(4-(4-ethoxyphenoxy)benzyl)-〇-7enylenediamine N-(4-(4-ethoxyphenoxy)benzyl) -〇-phenylenediamine 1.00Of,) ethylamine 0.8881 and anhydrous tetrahydrofuran 6 to 1
An anhydrous tetrahydrofuran solution containing 0.805 F of acetic anhydride was added dropwise at 0° C. for 80 minutes and stirred. After the dripping is finished,
After stirring at room temperature overnight, 100 ml of water was added, 200 d of ethyl ether was extracted in two portions, washed with water, dried over anhydrous sodium sulfate, ethyl ether was distilled off under reduced pressure, and extracted with toluene and hexane. By recrystallizing from a mixed solvent of
) 148.1°C) (7) N-acetyl-N'-(4-(
0.824f of 4-ethoxyphenoxy)benzylco-0-phenylenediamine was obtained.

■ Production of 1-(4-(4-ethoxyphenoxy)benzylco-2-methylbensimitasol) N-acetyl-N'-(4-(4-ethoxyphenoxy)benzyl)-〇-phenylene obtained in ■ Diamine 0
．． A mixture of 80f and 5 ml of acetic acid was heated to reflux with stirring for 2 hours, cooled to room temperature, and excess acetic acid was distilled off under reduced pressure. To the obtained oil was added 50 s of a 5% aqueous solution of hydroxide, and the mixture was extracted with 100 ml of toluene.

After washing with water, it was dried over anhydrous sodium sulfate, toluene was distilled off under reduced pressure, and subjected to silica gel column chromatography (-) to obtain 0.70 f of the target compound (81).

Reference Example 6 Production of compound (81) ■ Production of N-acetyl-N'-(4-(4-ethoxyphenoxy)benzyl)-〇-phinydiamine N-acetyl-N'-(4-(4 -ethoxyphenoxy)benzylidene]-〇-phenylenediamine 1.50 y, platinum oxide 0.10 f, acetic acid 1.
6d and ethanol 15+w/ under stirring,
Hydrogen gas was added. When hydrogen gas was no longer absorbed, the reaction system was replaced with nitrogen gas, the reaction mixture was passed through the mouth, the platinum oxide catalyst was removed, and ethyl ether 1
00d, washed with water, saturated hydrogen carbonate), washed with an aqueous IJ solution, further washed with water, dried over anhydrous sodium sulfate, ethyl ether was distilled off under reduced pressure, and subjected to silica gel column chromatography to obtain white crystals. (mp148
．． 1° C.) (7) 1.25 f of N-y*thyl-Nz-(4-(4-ethoxyphenoxy)benzyl)-〇-phenylenediamine was obtained.

■ 1-(4-(4-ethoxyphenoxy)benzylco-2-methylbenzimidazo-'. Manufacture
(N-acetyl- obtained in
The target compound (81 ) 0.89 f was obtained, Reference Example 7
Production of compound (81) Φ Production of N-acetyl-Nl-C4-C4-ethoxyphenoxy)benzylidene]-〇-phenylenediamine N-7 Cetyl-O-phenylenediamine 1.502 f% p-)reninsulfonic acid 0.05f,
4-(4-ethoxyphenoxy)benzaldehyde2.
A mixture of 428 F. After washing with an aqueous solution, washing with water and drying with anhydrous sodium sulfate, toluene was distilled off under reduced pressure, and the solvent was completely removed using a vacuum pump to obtain white crystals (mp 152.6°C) of N-acetyl- 8.79f of Nl-C4-C4-ethoxyphenoxy)benzylidene]-〇-7enylenediamine was obtained.

■ Production of 1-(4-(4-ethoxyphenoxy)benzylco-2-methylbenzimidazole) N-acetyl-Nl-C4-(4-ethoxyphenoxy)benzylidene]-〇-phenyl diamine obtained in ■ By performing the same reaction operation as in Reference Example 6 (■) at 1.50V, white crystals of N-acetyl-N'-(4-(
4-ethoxyphenoxy)benzyl]-〇-phenylenediamine 1.25F was obtained, and then this and acetic acid 5
By carrying out the same reaction operation as in Example 2 (■) using ml, the target compound (81) 1.12
I got an F.

Reference Example S Preparation of compound (85) N-acetyl-Nl-(4-(4-chloro-8-methylphenoxy)benzyl)-0-phenyl diamine 8.
The mixture with 20w1 of 0 Of tolf acid was heated under reflux with stirring for 2 hours, then cooled to room temperature, and acetic acid was distilled off under reduced pressure. 100 d of 6% aqueous sodium hydroxide solution was added to the obtained oil, and extracted with toluene 100 ml. After washing with water, it was dried over anhydrous sodium sulfate, toluene was distilled off under reduced pressure, and the mixture was subjected to silica gel column chromatography to obtain 2.27 t of the target compound (85) as a colorless liquid (nD 1.6175). Ta.

Reference Example 9 Production of Compound (6) Ethyl N-(2-(4-(4-)lyloxy)benzylamino]phenyl]formimidate 0.5Of and formic acid 5
After heating the mixture with ml to reflux under stirring for 3 hours,
The mixture was cooled to room temperature, and the formic acid was distilled off under reduced pressure. To the obtained oil was added 50+w/w of a 6% hydroxylated IJum aqueous solution, and extracted with 60d of toluene. After washing with water, drying with anhydrous sodium sulfate, distilling off toluene under reduced pressure, and subjecting to silica gel column chromatography, white crystals (
Compound (5) which is the target product of mp 210°C) 0.4
Obtained 1F.

Next, Table 1 shows some of the compounds of the present invention produced according to the production methods shown in these Examples and Reference Examples.

Table 1 General formula In order to demonstrate the usefulness of the benzimidazole derivatives of the present invention as insecticidal and acaricides, insecticidal and acaricidal test examples are given below as reference examples.

The benzimidazole derivatives are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 Compound symbol Structural formula Name Ag
ric, Biol, Chan.

Compound Symbol Structural Formula Name Reference Example 10 An emulsion of the following benzimidazole derivative obtained according to the following formulation example was diluted with water to a concentration of 8.5 ppm. 100 ml of the diluted solution was put into a 180 ml polycup, and 20 last-instar larvae of A. crucianum were released. The survival and death of the animals was investigated on the day after release.

After that, food was added to each plot, and when all of the untreated plots had emerged, the inhibition rate of emergence was investigated. The results are shown in Table 8.

The mortality rate and emergence inhibition rate were each divided into the following eight levels and displayed.

(Death rate) A: 9G% or more B: Less than 90% to 10
% C: Less than 10% (molding inhibition rate) A: 99% or more B: Less than 90% ~
80% C: Less than 80% [Formulation Example] 10 parts of a benzimidazole derivative, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene are thoroughly mixed to obtain an emulsion.

Table 8 Reference Example 11 -
10 adult female spider mites per leaf, 2
It was stored in a constant temperature room at 5°C. After 6 days, an emulsion of the following benzimidazole derivative and a control compound prepared according to the formulation example described in Reference Example 10 was mixed with water to a concentration of 500 p of the active ingredient.
The solution was diluted to 100 pm and sprayed on a turntable at 10 d per pot, and at the same time 2 d was irrigated into the soil.

Eight days later, the degree of damage caused by spider mites to each plant was investigated. The results are shown in Table 4.

The effectiveness criteria were divided into the following 8 levels and displayed.

m: Almost no damage was observed.

+: Slight damage is observed.

廿: The same damage as in the untreated area was observed. Ru.

Table 4

Claims (1)

[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_2 and R_3 are the same or different, and are hydrogen atoms, halogen atoms, nitro groups, cyano groups, or optionally substituted Lower alkyl group, lower alkenyl group, lower alkynyl group, lower cycloalkyl group, lower alkoxy group, lower alkenyloxy group, lower alkynyloxy group, lower cycloalkoxy group, lower alkylthio group, lower alkenylthio group, lower alkynylthio group group, a lower cycloalkylthio group, a lower dialkylamino group, a lower alkylsulfonyl group, or a lower alkylsulfinyl group, and R_2 and R_3 are bonded at the terminals to add 0 to 2 oxygen atoms or sulfur atoms into the ring. An optionally substituted saturated or unsaturated 5- or 6-membered ring can be formed. X represents an oxygen atom, a sulfur atom, a methylene group, a sulfonyl group, a sulfinyl group or an imino group. ] Aniline derivatives and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_1 represents a hydrogen atom or a lower alkyl group. ] A general formula characterized by reacting with a carboxylic acid or its reactive derivative represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, R_2, R_3 and X represent the same meanings as above. . ] A method for producing a benzimidazole derivative represented by