JPH02212484A - Trihaloimidazole derivative, production thereof and insecticide comprising the same derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (X<1> to X<3> are halogen). USE:An insecticide showing high insecticidal activity against insect pests of the order Dictyoptera and dipterous insect pests. PREPARATION:A trihaloimidazole shown by formula II is reacted with 2- chloro-5-pyridylmethyl chloride preferably in an equivalent ratio of 1:1-1.2 in the presence of a dehydrogenating agent (e.g. pyridine) usually in an inert solvent such as hexane at 0-150 deg.C for 1-24 hours.

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Applications The present invention relates to a novel trihaloimidazole derivative, a method for producing the same, and an insecticide containing the same as an active ingredient.

<Prior Art> It is known that certain tribaloydazole derivatives are useful as active ingredients in acaricides or nematicides.

For example, in West German Patent No. 2081400,
1-(4-chlorobenzyl')-2,4,5-trichloroimidazole is also used as an acaricide, and 1-(4-chlorobenzyl)-2-bromo-4, It has been described that 5-cyclooimidazole is used as a nematocide.

<Problems to be Solved by the Invention> However, these compounds cannot always be said to be sufficient as active ingredients of the insecticide targeted by the present invention.

Means for Solving the Problems In view of the above circumstances, the present inventors have conducted intensive studies to develop a powerful insecticide. It has an insecticidal effect against many pests such as German cockroach, American cockroach, black cockroach, Japanese cockroach, Japanese cockroach, and other cockroaches.

Therefore, the compound of the present invention can be used as an active ingredient of an insecticide effective against pests that are a problem in many situations.

The compound of the present invention represented by the general formula (1) is a trihaloimidazole derivative (hereinafter referred to as the compound of the present invention) represented by -max (in the formula, x', x' and xl represent the same or different halogen atoms). ) was found to have strong insecticidal activity, and the present invention was completed.

(In the formula, xJ, xM and xJ represent the same meanings as above.) Produced by reacting trihaloimidazole represented by the following with 2-chloro-5-pyridylmethyl chloride in the presence of a dehydrohalogenating agent. can do.

The amounts of reagents used in the reaction are 1 to 1.2 equivalents of 2-chloro-6-pyridylmethyl chloride and 1 to 2 equivalents of dehydrohalogenation agent per 1 equivalent of tribaloydazole represented by -maximum (II). .4 equivalents, and these are 0 to 160
React at ℃ for about 1 to 24 hours.

This reaction is usually carried out in an inert solvent, and the solvents used include, for example, aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, and xylene, chloroform, Halogenated hydrocarbons such as carbon tetrachloride, dichloroethane, chlorobenzene, and dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone, and formic acid. Esters such as ethyl, ethyl acetate, butyl acetate, diethyl carbonate, nitrides such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile,
Tertiary amines such as pyridine, trietheramine, N,N-diethylaniline, tributylamine, N-methylmorpholine, formamide, N,N-dimethylforma (
Examples thereof include acid oxides such as di-, N-, N-dimethylacetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, and mixtures thereof.

Examples of the dehydrohalogenation agent include organic bases such as pyridine, triethylamine, and N,N-diethylaniline; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride; sodium methoxide; Examples include alkali metal alkoxides such as sodium ethoxide.

After the reaction is completed, usual post-treatments are carried out, and if necessary, purification can be carried out by chromatography, distillation, recrystallization, etc.

Examples of the trihaloimidazole represented by the general formula (I[) which is a raw material compound include 2.4.5-tribromoimidazole, 2-bromo-4,5-dichloroimidazole, 2.4.5-trichloroimidazole, etc. can be given. These raw material compounds are J, Hetero
Cyel, Chem, 4 899 (1967)
It can be manufactured by the manufacturing method described in et al.

In addition, 2-chloro-5-pyridylmethyl chloride is J
, Heteroeyel, Cbexyi, 1
6.8.88 (1979).

When the compound of the present invention is used as an active ingredient of an insecticide, it is usually mixed with a solid carrier, liquid carrier, gaseous carrier, or bait, or impregnated into a substrate such as a mosquito coil or mat, and then used as needed. Complementary to surfactants and other formulations! M71 can be added to oil preparations, emulsions, wettable powders, suspensions in water, emulsions in water, etc., granules, powders, aerosols, and mosquito coils. Electric mosquito repellent mat.

Heating fumigants such as No-Mat, self-combusting fumigants.

Chemically reactive fumigator. It is used in formulations such as heated smoking agents such as porous ceramic plate smokers, non-heated evaporative agents such as resin transpiration agents and impregnated paper evaporation agents, fumigants such as fugitives, ULV agents, S baits, etc.

These preparations usually contain 0.001-96% by weight of the compound of the present invention as an active ingredient.

Solid carriers used in formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, fubasamiclay, acid clay, etc.), talc, cera 12, and other inorganic minerals. (Sericite, 6
moxibustion, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.),
Examples include fine powders or granules of chemical fertilizers (ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea, ammonium chloride, etc.), and liquid carriers include:
For example, water, alcohols (meth, alcohol, ethanol, etc.), ketones (acetoni/, mether ethyl ketone,
etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphtha!non, etc.).

Aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.) etc.), yeast a El-? Kind (N.

N-dimethylformamide, N, N-, ~ dimethyl acedoylamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethylformamide, vegetable oils such as soybean oil, nut oil, etc. Examples of gaseous carriers, that is, propellants include chlorofluorocarbon gas, butane gas, LPG (petroleum gas), dimethyl ether, carbon dioxide gas, and the like.

Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers and their polyoxyethylenic products, polyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohol derivatives. etc. can be mentioned.

For example, casein, gelatin, polysaccharides (starch powder,

gum arabic, cellulose conductor, alginic acid, etc.).

Examples include lignin derivatives, bentonite, sugars, and synthetic water-soluble polymers (4-vinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), and examples of stabilizers include PAP (isopropyl acid phosphate), BHT (
2,6-di--tert-butyl4 J' f
Lua E) - Le), B HA (2tar t -
Examples include mixtures of butyl-4-methoxyphenol and 9-tart-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like.

Examples of the base material for mosquito coils include mixtures of raw plant powders such as wood flour and lees powder with binders such as tab flour, starch, and gluten.

The base material for the electric mosquito repellent mat may be, for example, a fibril made of cotton linter or a mixture of cotton linter and pulp that is compacted into a plate shape.

Examples of base materials for self-combusting smoke agents include nitrates, nitrites, guanidine salts, potassium salts, nitrocellulose, ethyl cellulose, combustion exothermic agents such as wood powder, alkali metals 1ζ, and alkaline earth metals. Gloss decomposition stimulants such as precious gold salts, electrochromates, and chromates, acidifying agents such as potassium nitrate, combustion support agents such as melamine and wheat starch, fillers such as diatoms, binders such as synthetic glues, etc. can be given.

The base materials for chemically reactive smoke agents include, for example, exothermic agents such as alkali metal sulfides, polysulfides, hydrosulfides, hydrated salts, and calcium oxide, and catalyst agents such as carbonaceous substances, iron carbide, and activated clay. , organic blowing agents such as azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenelentithramine, polystyrene, and polyurethane, and fillers such as natural fiber pieces and synthetic fiber pieces.

Examples of the base material of the non-heating transpiration agent include thermoplastic resin,
Examples include filter paper and Japanese paper.

Examples of base materials for poison bait include grain flour, vegetable essential oil, sugar,
Feed ingredients such as crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, agents to prevent accidental ingestion such as chili pepper powder, cheese flavoring, onion flavoring, peanut oil, etc. Examples include attractants.

The formulation of flowables (suspensions or emulsions in water) generally consists of 1-76% compound, 0.5-16% dispersing agent, 0.1-10% suspending aid (e.g. colloids and compounds imparting thixotropy), 0 to 10% of suitable auxiliaries (e.g. antifoaming agents, rust preventives, stabilizers,
Spreading agent, penetration aid 1. antifreeze agents, antibacterial agents, antifungal agents, etc.)
obtained by finely dispersing it in water containing

It is also possible to use an oil in which the compound hardly dissolves in place of water to form a suspension in oil. Examples of protective colloids used include gelatin, casein, gums, cellulose ether, and polyvinyl alcohol. Examples of compounds that impart thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, and polyacrylic acid.

The preparation thus obtained is used as it is or diluted with water or the like. It may also be used with or without mixing with other insecticides, acaricides, nematicides, soil pest control agents, fungicides, herbicides, plant growth regulators, synergists, fertilizers, and soil conditioners. It can also be used at the same time.

When the compound of the present invention is used as an active ingredient of an agricultural insecticide, the application rate is usually 6 to 500 F per 10 ares,
When applying emulsions, wettable powders, flowables, etc. after diluting them with water, the application concentration is 10 to 2009 ppm, and granules, powders, etc. should not be diluted in any way (they should be applied as they are). When used as an active ingredient in household and epidemic prevention insecticides, emulsions, wettable powders, flowables, etc.
o, oo.

Apply diluted to ppm, oil, aerosol, fumigant,
Fumigants, smoke retardants, ULV agents, poisonous baits, etc. should be applied as is.

These application amounts and concentrations vary depending on the type of formulation, application time, application location, application method, type of pest, degree of damage, etc., and may be increased or decreased without regard to the above range. can do.

<Examples> The present invention will be explained in more detail below using production examples, formulation examples, and test examples, but the present invention is not limited to these examples.

First, a production example of the compound of the present invention will be shown.

Production Example 1 [Production of compound (1) of the present invention] 2.4.5-
2,4,5-Trichloroydazole prepared from dazole (0,692.4 mmol) and sodium hydride (96 mmol, 4 mmol) was added to a DMF solution (6-) of the sodium salt of 2,4,5-trichloroydazole. -Chloro-5-pyridylmethyl chloride (0.65f, 4 mmol) was added dropwise.

After stirring at room temperature for 1 hour, 504 water was added to the reaction mixture and extracted with ether (80dX8). The ether skin was dried with magnesium sulfate and concentrated. The oily substance obtained by concentration was purified by silica gel column chromatography to obtain 0.6 (l) of the present compound (1).

m, 9. 96°C Next, Table 1 shows some of the compounds of the present invention produced according to this production method.

Table 1 shows formulation examples. The compounds of the present invention are indicated by the compound numbers listed in Table 1, and parts represent parts by weight.

Formulation Example 1 10 parts each of emulsion compounds (1) to (4) were dissolved in 85 parts of xylene and 85 parts of dimethylformide, and 14 parts of polyoxyethylenestyrylphenyl dichloroethyl and 6 parts of calcium dodecylbenzenesulfonate were dissolved. and stir well to obtain each IOX emulsion.

Formulation Example 2 20 parts of wettable powder compound (1) was added to a mixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic hydrated silicon oxide fine powder, and 54 parts of diatomaceous earth, and the mixture was added to a juice mixer.・Adjust stirring to obtain 20X wettable powder.

Formulation Example 8 Granules (in the case of solid drug substance) Compound (5 parts of odor, 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 8 parts of bentonite)
Add 0 parts and 55 parts of clay and mix thoroughly. Then, an appropriate amount of water is added to these molten metals, which are further stirred, granulated using a granulator, and dried through ventilation to obtain 5% granules.

Formulation Example 4 Dissolve 1 part of the powder compound (1 part fat) in an appropriate amount of acetone, add 0.8 part of synthetic hydrated silicon oxide fine powder, 0.8 part of PAP, and 98.7 parts of clay, and dissolve in a juice extractor. Mix by stirring and remove acetone by evaporation to obtain IX powder.

Formulation Example 570 Able formulation (in the case of solid drug substance) Compound (4)
20 parts of sorbitan trioleate and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of a water-soluble FF containing 2 parts of polyvinyl alcohol, and after finely pulverizing the mixture with a sand grinder (particle size of 8P or less), 0.2 parts of xanthan gum was added. 5.40 parts were added to an aqueous solution containing 06 parts of aluminum magnesium silicate and 041 parts of aluminum magnesium silicate, and further 10 parts of propylene glycol were added and mixed with stirring to obtain a 20% suspension in water.

Formulation Example G Oil agent 0.1 part of each of compounds (1) to (4) is dissolved in 10 parts of trichloroethane, and this is mixed with 89.9 parts of kerosene to obtain a 0.1% oil agent.

Formulation Example 7 Oil-based aerosol compound (1) 0.1 part, tetramethrin 062 parts, d
--- Mix and dissolve 0.1 part of phenothrin, 10 parts of trichloroethane, and 69.6 parts of kerosene, fill it into an aerosol container, attach the valve part, and then inject 80 parts of propellant (liquefied petroleum gas) through the pulp part. Add to 5hi.

Pressure filling to obtain a hydraulic aerosol.

Formulation Example 8 Mosquito coil compound (2) 0.8 S' and d-allethrin 0°aL
Add I. .

Dissolved in 20% of acetone, stirred and mixed uniformly with 99.42% of carrier for mosquito control wire (mixing tab powder: lees powder: wood flour in the ratio of 4:8:8), and then adding 120% of water. The thoroughly kneaded mixture is molded and dried to obtain mosquito coils.

Formulation Example 9 Heat smoke agent compound (1)... 100'''9 of each of (4) was dissolved in an appropriate amount of acetone, 4°Q alX 4.0 cm,
, a porous ceramic plate with a thickness of 1.2G is impregnated to obtain a hot smoking agent.

Next, test examples will show that the compounds of the present invention are useful as active ingredients of insecticides. Note that the compound of the present invention is
The compound number in the table is used as a reference, and the compound used for comparison is the second one.
Indicated by compound symbol in the table.

Table 2 The results are shown in Table 8.

Table 8 Test Example 1 (Insecticidal test against house fly) Diameter 6.51
1. Place a filter paper of the same size on the bottom of a polyethylene cup. The test compound was made into an emulsion according to Formulation Example 1, and the emulsion was mixed with water for 20 minutes.
A 0.7-fold diluted solution (300 ppm) was dropped onto a filter paper, and 80 liters of bait was added thereto.10 female adult house flies were released into the filter paper, and the lid was closed. After a period of time, the animals were examined to see if they were alive or dead, and the survival rate was determined (2 repetitions).

Test Example 2 10 adult German cockroaches (5 males and 5 males) were placed in a polyethylene cup of 9 diameters with a thin layer of Vaseline applied to the wall.
The fish were released, and then smothered with 16 mesh nylon gauze.
It was installed at the bottom of an acrylic cylinder with an inner diameter of 10 mm and a height of 87 cm. 0 of the test compound obtained according to Formulation Example G
．． Each 0.6-liter of 1X oil was sprayed directly from the top of the cylinder using a spray gun at a pressure of 0.6 atmospheres. After 10 minutes, the number of test insects knocked down was investigated, and the knockdown insect rate was determined (2 repetitions).

The results are shown in Table 4.

0.0125% of each of the compounds in Table 4 was sprayed directly from the upper end of the cylinder using a spray gun at a pressure of 0.6 atmospheres. After 20 minutes, the test insects were collected in a new container, fed with water and fed, and the survival rate was determined after 8 days to determine the survival rate (2 repetitions).

The results are shown in Table 6.

Table 5 Test Example 8 A thin layer of Vaseline was applied to the wall surface. 10 adult German cockroaches (6 males and 6 females each) of a pyrethroid-insensitive strain were released into a polyethylene cup with a diameter of 9, and the lid was covered with 16 mesh seeds. Elli X O#,
It was installed at the bottom of an acrylic cylinder with a height of 870 mm. Test obtained according to Formulation Example 6 (Effects of the Invention) The compound of the present invention exhibits high insecticidal activity against various pests such as #5 Pteran pests and Diptera pests, and is particularly effective in terms of rapid action. Are better.

Claims (4)

[Claims] (1) Trihaloimidazole derivative represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, X^1, X^2 and X^3 represent the same or different halogen atoms.) (2) Trihaloimidazole and 2-chloro represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, X^1, X^2 and X^3 represent the same or different halogen atoms.) 2. The method for producing a trihaloimidazole derivative according to claim 1, which comprises reacting the trihaloimidazole derivative with -5-pyridylmethyl chloride. (3) An insecticide comprising the trihaloimidazole derivative according to claim 1 as an active ingredient. (4) An insecticidal method using the trihaloimidazole derivative according to claim 1.