JPH0533221B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] [In the formula, R ₁ represents a hydrogen atom or a lower alkyl group, R ₂ and R ₃ are the same or different,
Hydrogen atom, halogen atom, nitro group, cyano group, or optionally substituted lower alkyl group, lower alkoxy group, lower alkenyloxy group, lower alkynyloxy group, lower alkylthio group, lower alkenylthio group, lower alkynylthio group represents a group or a lower alkylsulfonyl group,
In addition, by bonding R ₂ and R ₃ at the terminal,
Optionally substituted saturated or unsaturated 5 containing 0 to 2 oxygen atoms or sulfur atoms in the ring
A membered ring or a six-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. ] The present invention relates to a benzimidazole derivative represented by (hereinafter referred to as the compound of the present invention) and an acaricide containing the same as an active ingredient. Agric.Biol.
Chem., 46 (6) 1715 (1982).
However, these compounds are not necessarily sufficient as active ingredients for insecticides, and their acaricidal efficacy is also poor. The present inventors have conducted extensive studies to develop a compound with excellent insecticidal and acaricidal effects, and as a result, have confirmed that the compound of the present invention is particularly excellent in acaricidal efficacy, and have completed the present invention. . That is, the compound of the present invention can be applied to spider mites,
It has excellent acaricidal efficacy against spider mites such as orange spider mites, and is also highly effective against spider mites that have developed resistance to existing acaricides, making it an active ingredient in acaricides for agriculture and horticulture. It can be used as In the compound of the present invention represented by the general formula [], R ₂ and R ₃ are described in more detail as follows. That is, as R ₂ and R ₃ ,
Hydrogen atom, halogen atom, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkenyloxy group having 2 to 6 carbon atoms, alkynyloxy group having 2 to 6 carbon atoms, carbon atom Number 1~
6 alkylthio group, an alkenylthio group having 2 to 6 carbon atoms, an alkynylthio group having 2 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms,
Haloalkyl group having 1 to 6 carbon atoms, haloalkoxy group having 1 to 6 carbon atoms, haloalkenyloxy group having 2 to 6 carbon atoms, haloalkynyloxy group having 2 to 6 carbon atoms, haloalkynyl group having 1 to 6 carbon atoms, 6 haloalkylthio group, haloalkenylthio group having 2 to 6 carbon atoms, haloalkynylthio group having 2 to 6 carbon atoms, haloalkylsulfonyl group having 1 to 6 carbon atoms, alkoxyalkyl group having 2 to 6 carbon atoms group, haloalkoxyalkyl group having 2 to 6 carbon atoms, alkylthioalkyl group having 2 to 6 carbon atoms, haloalkylthioalkyl group having 2 to 6 carbon atoms, alkoxyalkoxy group having 2 to 6 carbon atoms, carbon atom Haloalkoxyalkoxy group having 2 to 6 carbon atoms, alkenyloxyalkyl group having 3 to 6 carbon atoms, alkynyloxyalkyl group having 3 to 6 carbon atoms, alkenyloxyalkoxy group having 3 to 6 carbon atoms, 3 carbon atoms ~6 alkynyloxyalkoxy groups, alkoxyalkylthio groups having 2 to 6 carbon atoms, alkylthioalkylthio groups having 2 to 6 carbon atoms, or alkylthioalkoxy groups having 2 to 6 carbon atoms, 3,4-methylenedioxy groups, 3,4-difluoromethylenedioxy group, 3,4-trifluoroethylenedioxy group,
Examples include 3,4-trimethylene group and 3,4-tetramethylene group. Among the compounds of the present invention represented by the general formula [], preferred are compounds in which R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ are the same or different,
Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylthio group having 1 to 6 carbon atoms,
X is a compound representing an oxygen atom, a sulfur atom, a methylene group or a sulfonyl group. The compound of the present invention has the general formula [] [In the formula, R ₁ represents the same meaning as above. ] Benzimidazole compound shown by and general formula [] [In the formula, R ₂ , R ₃ and X have the same meanings as above, and Y represents a halogen atom, a tosyloxy group or a mesyloxy group. ] It can be produced by reacting a substituted benzyl compound shown in the following in the presence of an acid binder. In this method, the acid binder includes, for example, alkali metals such as lithium, sodium, and potassium, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal amides such as sodium amide, sodium hydroxide, and potassium hydroxide. Alkali metal hydroxides, sodium carbonate, etc.
Examples include alkali metal carbonates such as potassium carbonate, and organic bases such as triethylamine and N,N-diethylaniline. This reaction can be carried out in the presence or absence of a solvent, but is usually carried out at -30°C in the presence of a solvent.
to the boiling point of the reaction mixture, generally from 0℃ to 110℃
Perform within the range of The reaction is generally complete in 0.5 to 50 hours. Examples of solvents include water, hydrocarbons such as benzene, toluene, and xylene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and dimethoxyethane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and dimethyl. Examples include acid amides such as formamide, diethylformamide, and dimethylacetamide, dimethylsulfoxide, and mixtures thereof. In addition, in this reaction, a phase transfer catalyst such as benzyltriethylammonium chloride and tetrabutylammonium bromide can also be used. In this reaction, the molar ratio of the benzimidazole compound represented by the general formula [] to the substituted benzyl compound represented by the general formula [] is 1:0.1.
~10, but usually 1:0.8~1.0. Further, the molar ratio of the benzimidazole compound represented by the general formula [] to the acid binder is suitably 1:0.9 to 1.1. After the reaction is completed, usual post-treatments are carried out, and if necessary, purification is carried out by chromatography, distillation, recrystallization, etc. The compounds of the present invention also include inorganic acid salts such as hydrochloric acid and sulfuric acid, and organic acid salts such as trifluoroacetic acid of the benzimidazole derivative of the general formula []. Examples of the benzimidazole compound represented by the general formula [] include benzimidazole,
Examples include 2-methylbenzimidazole and 2-ethylbenzimidazole. Further, the substituted benzyl compound represented by the general formula [] is known or can be easily produced by a method similar to a known method. Specific examples thereof are shown below, but the invention is not limited to the examples. That is, 4-phenoxybenzyl bromide,
4-(3-tolyloxy)benzyl chloride, 4
-(4-n-pentylphenoxy)benzyl chloride, 4-(4-ethoxyphenoxy)benzyl chloride, 4-(3-ethoxyphenoxy)benzyl chloride, 4-(4-methylthiophenoxy)
Benzyl chloride, 4-(4-vinyloxyphenoxy)benzyl chloride, 4-(3-chlorophenoxy)benzyl chloride, 4-(2-fluorophenoxy)benzyl p-toluenesulfonate, 4-(3- fluorophenoxy)benzyl bromide, 4-(3-isopropylphenoxy)
Benzyl chloride, 4-(3-n-propylthiophenoxy)benzyl chloride, 4-(4-methylsulfonylphenoxy)benzyl chloride, 4
-(3-trifluoromethylphenoxy)benzyl bromide, 4-(2-chlorophenylthio)benzyl bromide, 4-(3-bromophenoxy)
Benzyl bromide, 4-(4-ethylphenoxy)
Benzyl chloride, 4-(3-ethylphenoxy)
Benzyl chloride, 4-(3-n-propoxyphenoxy)benzyl chloride, 4-(3-n-butoxyphenoxy)benzyl chloride, 4-(3
-n-pentyloxyphenoxy)benzyl chloride, 4-(4-isopropylthiophenoxy)
Benzyl chloride, 4-(3-n-propylphenoxy)benzyl chloride, 4-(4-isopropylphenoxy)benzyl chloride, 4-benzylbenzyl methanesulfonate, 4-(3-ethylthiophenoxy)benzyl Chloride, 4-
(4-Methoxymethylphenoxy)benzyl chloride, 4-(4-n-butylthiophenoxy)benzyl chloride, 4-(4-difluoromethoxyphenoxy)benzyl chloride, 4-(4-n-propylphenoxy) enoxy)benzyl chloride, 4-(4
-n-butylphenoxy)benzyl chloride, 4
-(4-n-propoxyphenoxy)benzyl chloride, 4-(4-sec-butylphenoxy)benzyl chloride, 4-(2,5-dimethylphenoxy)benzyl chloride, 4-(2,3-dimethylphenoxy)benzyl chloride enoxy)benzyl chloride, 4-(3,5-
difluorophenoxy)benzyl chloride, 4-
(4-n-butoxyphenoxy)benzyl chloride, 4-(4-n-pentylthiophenoxy)benzyl chloride, 4-(3,4-methylenedioxyphenoxy)benzyl chloride, 4-(4 -allylthiophenoxy)benzyl chloride, 4-
(3-allyloxyphenoxy)benzyl chloride, 4-(4-propargyloxyphenoxy)
Benzyl chloride, 4-(4-n-hexylphenoxy)benzyl chloride, 4-(3-n-hexyloxyphenoxy)benzyl chloride, 4-
(3-isopropoxyphenoxy)benzyl chloride, 4-(3-ethynyloxyphenoxy)benzyl chloride, 4-(4-allylthiophenoxy)benzyl chloride, 4-[4-(2,2- dichlorovinyloxy)phenoxy]benzyl chloride, 4-[4-(1,1,2,2-tetrafluoroethoxy)phenoxy]benzyl chloride, 4-
(3-chloro-4-methylphenoxy)benzyl chloride, 4-(3,4-difluoromethylenedioxyphenoxy)benzyl chloride, 4-(4
-sec-pentylphenoxy)benzyl chloride,
4-(4-methoxymethylthiophenoxy)benzyl chloride, 4-[4-(2,2,2-trifluoroethoxy)phenoxy]benzyl chloride,
4-(4-ethoxymethylphenoxy)benzyl chloride, 4-(3-trifluoromethylthiophenoxy)benzyl chloride, 4-(3-methoxy-4-methylphenoxy)benzyl chloride,
4-(4-ethyl-2-methylphenoxy)benzyl chloride, 4-(2-methyl-4-n-propylphenoxy)benzyl chloride, 4-(4-
n-Butyl-2-methylphenoxy)benzyl chloride, 4-(3-methoxyphenoxy)benzyl chloride, 4-(4-isopropoxyphenoxy)benzyl chloride, 4-(4-sec-butoxyphenoxy) Benzyl chloride, 4-(4-n-
pentyloxyphenoxy)benzyl chloride,
4-[4-(1-ethoxyethyl)phenoxy]benzyl chloride, 4-(3-allylthiophenoxy)benzyl chloride, 4-(3-allyloxymethylphenoxy)benzyl chloride, 4-(4
-ethoxyphenylthio)benzyl chloride, 4
-(3-ethynyloxymethylphenoxy)benzyl chloride, 4-(4-methylthiomethylthiophenoxy)benzyl chloride, 4-(4-isobutylthiophenoxy)benzyl chloride, 4-
[4-(2-methylallyloxy)phenoxy]benzyl chloride, 4-(3-ethylsulfonylphenoxy)benzyl chloride, 4-[4-(1,1
-dichloro-2,2-difluoroethoxy)phenoxy]benzyl chloride, 4-(2-methyl-
4-n-propoxyphenoxy)benzyl chloride, 4-(2-chloro-4-ethoxyphenoxy)
Benzyl chloride, 4-[4-(2-butenyloxy)phenoxy]benzyl chloride, 4-[4-
(1-methylallyloxy)phenylthio]benzyl chloride, 4-(3-ethoxyanilino)benzyl chloride, 4-(5,6,7,8-tetrahydro-2-naphthyloxy)benzyl chloride, 4-(4- bromo-3-chlorophenoxy)
Benzyl chloride, 4-(4-trifluoromethylphenoxy)benzyl chloride, 4-phenylsulfinylbenzyl bromide, 4-(3-nitrophenoxy)benzyl chloride, 4-(4-n
-propoxyphenoxy)benzyl chloride, 4
-(4-methoxyphenoxy)benzyl chloride,
4-(4-ethylthiophenoxy)benzyl chloride, 4-(4-n-propylthiophenoxy)
Benzyl chloride, 4-(3-methylthiophenoxy)benzyl chloride, 4-(3-n-butylthiophenoxy)benzyl chloride, 4-(4-
n-propoxyphenylthio)benzyl chloride, 4-(2,3-dihydrobenzofuran-5-
yloxy)benzyl chloride, 4-(2,3-
Dihydro-2,2-dimethylbenzofuran-5-
yloxy)benzyl chloride, 4-(indan-5-yloxy)benzyl chloride, 4-[4
-(1,2,2-trifluoroethoxy)phenoxy]benzyl chloride, 4-[4-(2-bromo-1,1,2,2-tetrafluoroethoxy)phenoxy]benzyl chloride, and the like. Next, a manufacturing example will be shown. Production example 1 10ml of anhydrous dimethylformamide and 0.14g of sodium hydride (62% oil suspension)
0.48 g (3.6 mmole) of 2-methylbenzimidazole was added to the mixture with (3.6 mmole) under stirring. After stirring at room temperature for 1 hour, it was cooled to 5-10°C, and the 4-
(3-Tolyloxy)benzyl bromide 1.00g
(3.6 mmole) in anhydrous dimethylformamide solution 5
ml was added dropwise over 30 minutes. After the addition, the mixture was stirred at room temperature overnight. After the reaction, the mixture was poured into 100 ml of water, extracted twice with 30 ml of toluene, washed with water, dried over anhydrous sodium sulfate, distilled off the toluene under reduced pressure, and subjected to silica gel column chromatography to form a colorless liquid (n ^27.0 _D) .
1.6112) of 2-methyl-1-[4-(3-tolyloxy)benzyl]benzimidazole [the compound of the present invention (31)] was obtained. Production example 2 Toluene 20ml, 2-methylbenzimidazole
0.55g (4.2mmol), triethylamine 0.42g
(4.2 mmol) and 1.00 g (3.8 mmol) of 4-(4-ethoxyphenoxy)benzyl chloride was stirred under reflux for 5 hours. After cooling to room temperature, it was washed with water, dried over anhydrous sodium sulfate, toluene was distilled off under reduced pressure, and subjected to silica gel column chromatography to obtain 1-[4-(4-ethoxy) as a colorless liquid (n ^26.0 _D 1.5984). 1.20 g of phenoxy)benzyl]-2-methylbenzimidazole [the compound of the present invention (50)] was obtained. Table 1 shows some of the compounds of the present invention that can be produced by such a production method.

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[Table] When the compound of the present invention is used as an active ingredient of an acaricide, it may be used as is without adding any other ingredients, but it is usually used as a solid carrier, liquid carrier, gaseous carrier, surfactant, etc. It can be mixed with formulation auxiliary agents, baits, etc., or impregnated into base materials such as incense sticks and mats to produce emulsions, wettable powders, powders, granules, oils, aerosols, mosquito coils, electric mosquito repellents, etc. It is formulated into heating fumigants, fogging agents such as fogging, non-heating fumigants, poison baits, etc. These preparations contain 0.01% to 95% by weight of the compound of the present invention as an active ingredient. Solid carriers include kaolin clay, attapalgite clay, bentonite, acid clay, pyrophyllite,
Talc, diatomaceous earth, calcite, corn cob flour,
There are fine powders or granules such as walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide, and liquid carriers include aliphatic hydrocarbons such as kerosene and kerosene,
Aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene, halogenated hydrocarbons such as dichloroethane, trichloroethylene, and carbon tetrachloride, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and cellosolve, acetone, methyl ethyl ketone, cyclohexanone, and isophorone. Ketones such as diethyl ether, dioxane, tetrahydrofuran and other ethers, esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide, vegetable oils such as soybean oil and cottonseed oil. etc. Gaseous carriers include fluorocarbon gas,
Examples include LPG (liquefied petroleum gas) and dimethyl ether. Surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, and naphthalene sulfone. Examples include anionic surfactants such as acid formalin condensates, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Formulation aids such as fixing agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein, gelatin, CMC (carboxymethylcellulose), pine oil, agar, etc. Stabilizers for,
Alkyl phosphates such as PAP (isopropyl acid phosphate) and TCP (tricresyl phosphate), vegetable oils, epoxidized oils, surfactants mentioned above, antioxidants such as BHT and BHA, fatty acids such as sodium oleate and calcium stearate. salt, methyl oleate,
Examples include fatty acid esters such as methyl stearate. Examples of formulations are shown below. In addition, the compound of the present invention is the first
Indicated by compound number in the table. Parts are parts by weight. Formulation Example 1 0.2 parts of the present compound (1) or (29), 2 parts of xylene, and 97.8 parts of white kerosene are mixed to obtain each oil agent. Formulation Example 2 Compounds of the present invention (1), (29) to (32), (36),
(37), (41) ~ (50), (52), (54), (55), (
60)
10 parts each of (66), 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene are thoroughly mixed to obtain each emulsion. Formulation Example 3 20 parts of the compound (7) or (66) of the present invention, 10 parts of fenitrothion, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 65 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to prepare each hydrating agent. get. Formulation Example 4 1 part of the compound of the present invention (10) or (31), 2 parts of carbaryl, 87 parts of kaolin clay, and 10 parts of talc
Thoroughly grind and mix these parts to obtain each powder. Formulation Example 5 5 parts of the compound of the present invention (15) or (50), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite, and 62 parts of kaolin clay.
After thoroughly pulverizing and mixing the two parts, adding water and kneading well, the mixture is granulated and dried to obtain each granule. These preparations can be used as they are or diluted with water. In addition, other insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers,
It can also be used in combination with soil conditioners and the like. When the compound of the present invention is used as an acaricide, the application amount is usually 5 g to 500 g per 10 ares, and when applied after diluting an emulsion, wettable powder, etc. with water, the application concentration is 10 ppm to 1000 ppm. and
Powders, granules, oils, aerosols, etc. should be applied in their original form without any dilution. Next, a test example is shown. Note that the compound of the present invention has the first
The compounds used for comparison are indicated by the compound numbers in the table, and the compounds used for comparison are indicated by the compound symbols in Table 2.

[Table] Test Example 1 Potted green beans (first leaf stage) 7 days after sowing were infested with 10 female adult spider mites per leaf and stored in a constant temperature room at 25°C. 6 days later,
An emulsion of the following compound of the present invention and a control compound prepared according to Formulation Example 2 was diluted with water so that the active ingredient was 500 ppm, and 10 ml per pot was sprayed on a turntable, and at the same time, 2 ml was poured into the soil. Eight days later, the degree of damage caused by spider mites to the green beans was investigated. The degree of damage was divided into the following three levels. -: Almost no damage is observed. +: Slight damage is observed. : The same damage as in the untreated area is observed.

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Claims (1)

[Claims] 1. General formula [In the formula, R ₁ represents a hydrogen atom or a lower alkyl group, R ₂ and R ₃ are the same or different,
Hydrogen atom, halogen atom, nitro group, cyano group, or optionally substituted lower alkyl group, lower alkoxy group, lower alkenyloxy group, lower alkynyloxy group, lower alkylthio group, lower alkenylthio group, lower alkynylthio group represents a group or a lower alkylsulfonyl group,
In addition, by bonding R ₂ and R ₃ at the terminal,
Optionally substituted saturated or unsaturated 5 containing 0 to 2 oxygen atoms or sulfur atoms in the ring
A membered ring or a six-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. ] A benzimidazole derivative represented by 2 General formula [In the formula, R ₁ represents a hydrogen atom or a lower alkyl group, R ₂ and R ₃ are the same or different,
Hydrogen atom, halogen atom, nitro group, cyano group, or optionally substituted lower alkyl group, lower alkoxy group, lower alkenyloxy group, lower alkynyloxy group, lower alkylthio group, lower alkenylthio group, lower alkynylthio group represents a group or a lower alkylsulfonyl group,
In addition, by bonding R ₂ and R ₃ at the terminal,
Optionally substituted saturated or unsaturated 5 containing 0 to 2 oxygen atoms or sulfur atoms in the ring
A membered ring or a six-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. ] A miticide characterized by containing a benzimidazole derivative represented by the following as an active ingredient.