JPS603300B2 - Imidazole derivatives and insecticides and acaricides - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to a novel compound and its use, and in detail -
General formula (1) (wherein, X, X2 and x3 are halogen atoms, Y is a halogen atom, lower alkyl group or lower alkoxy group,
n represents 0, 1 or 2; R and R2 represent a hydrogen atom, a lower alkyl group, a phenyl group or a penzyl group.

) and insecticides and acaricides containing the compounds as active ingredients. The object of the present invention is to provide an insecticide and acaricide that causes almost no phytotoxicity to plants, has a low clump-like effect on humans, livestock, and fish, and can be used safely.

The amount and variety of natural and synthetic agents used to control sanitary pests, plant pests, and plant parasitic mites have increased year by year, but they have been shown to cause phytotoxicity to cultured plants, acute rhododendrons to warm-blooded animals, and even more. There are few products that can be used safely due to long-term residual toxicity in turmeric plants and stored products.

In addition, insects and mites that are resistant to currently used drugs have recently appeared, making it extremely difficult to control them.
Therefore, there is a strong demand for the emergence of effective and economical pest control agents that can solve these problems. The present inventors synthesized a large number of organic compounds and conducted various biological tests, and found that the compounds represented by the general formula (1) are effective against sanitary pests, plant pests, and plant parasitic mites. It was discovered that it has excellent insecticidal and acaricidal efficacy, and furthermore,
The present invention was completed through repeated biological and physicochemical research.

Compounds similar to the compounds of the present invention include N,N-dimethyl-N'-(3,4-dinitrophenyl)-(4,5-dichloroimidazolyl)-[11-amidine, etc.
It is known as a herbicide and as having a weak acaricidal effect (Jikai Sho 50-13 Spot No. 3).

The compounds of the present invention have acaricidal efficacy of 2 to 1" higher than the above-mentioned known compounds, and have reduced chemical damage.

In particular, in the general formula (1), X, , X2 and x3
Compounds in which is a bromine atom and R and R2 are lower alkyl groups have no phytotoxicity and are excellent in efficacy.

In the production of the compound of the present invention, the general formula (〇) (wherein Y, n, R, and R2 have the same meanings as defined above) is used.

) and trihaloimidazole are reacted in an inert solvent in the presence of an acid binder. Examples of inert solvents include acetonitrile, acetone, and chlorine. Polar solvents such as roform, dichloromethane, dimethyl sulfoxide, and tetrahydrofuran are used, and sodium carbonate, potassium carbonate, sodium hydroxide, imidazole, trimethylamine, triethylamine, pyridine, and the like are used as acid binders. The reaction temperature is from 0 to 90 o'clock, preferably from room temperature to the boiling point of the solvent. The reaction time is 3 minutes to several hours. After the reaction is complete, if the salt of the acid binder is precipitated, it is separated and the solvent is distilled off. By dissolving the residual candle in a suitable solvent such as chloroform, washing with water, drying, and removing the solvent, a substantially pure compound of the present invention can be obtained in a good yield.
If necessary, it was further purified by recrystallization or column chromatography, and the structure was determined from the results of elemental analysis, IR spectrum, NMR spectrum, mass vector, etc. Next, the method for producing the compound of the present invention will be explained in more detail by giving a synthesis example.

Synthesis Example 1 (Compound No. 9) In 20 parts of acetonitrile, 2 parts of tripromimidazole and 1.9 parts of 4-chlorophenyliminochlorocarboxylic acid diethylamide hydrochloride were added, and 1.4 parts of triethylamine was added to a rope at room temperature. dripped.

After continuing to stir for 2 to 3 hours, the reaction solution was added to 200 ml of ice water, the precipitated white crystals were filtered out, and recrystallized from ethanol to give N.N-dimethyl-N-(4 -chlorophenyl)-(2,4,5-tribromoimidazolyl)-m-amidine 3 (yield 90%) was obtained. Melting point 8
7-900 Synthesis Example 2 (Compound No. 16) Tribromimidazole 2 and 2.
1.9 hours of 4-dichlorophenyliminochlorocarboxylic acid diethylamide hydrochloride was added, and further 1.4 hours of trimethylamine was added at room temperature.

After incubating for 3 hours, the reaction product was poured into 200 °C of ice water, the precipitated crystals were concentrated, and recrystallized from ethanol to give N.N-dimethyl-N'-(2,4-dichlorofluorophore). (yield: 88%). Melting point 1
43-4°C Synthesis Example 3 (Compound No. 2) Into 20 ml of acetonitrile were added 3 ml of tribromoimidazole and 2.7 ml of 2-methyl-4-chlorophenyliminochlorocarboxylic acid diethylamide hydrochloride.

Further, two portions of trimethylamine were added to the bottom of the azure at room temperature, and the azure was continued for 3 hours. After that, apply the reaction solution to 200 skin [
The crystals precipitated by dipping in ice water were taken and recrystallized from ethanol to obtain N・N-dimethyl-N'-(2-methyl-4
-chlorophenyl)-(2,4,5-tripromoimidazolyl)'1'-amidine (4.1 units (yield: %)) was obtained. Melting point: 172-4°C (decomposed) Table 1 shows the structural formulas and physical constants of representative compounds of the present invention.

Table 1 General formula '1} The insecticide and acaricide of the present invention can be used with the active ingredient compound as delivered, and for the purpose of using it as an agricultural chemical, it can be used in the form that general agricultural chemicals can take, that is, as a hydrating powder. , granules, powders,
It can be used in the form of an emulsion or the like.

As additives and carriers, when intended as a fixative,
Vegetable powders such as soybean flour and wheat flour, and mineral fine powders such as diatoms, apatite, gypsum, turk, pyrophyllite, and clay are used. When a liquid dosage form is intended, kerosene, key oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, water, etc. are used as the solvent. In these preparations, a surfactant may be added if necessary in order to obtain a uniform and stable form. The wettable powders and emulsions thus obtained are diluted with water to a predetermined concentration and used as a suspension or emulsion, and the powders and granules are sprayed on plants as they are. Next, examples of formulations will be shown, but the carrier, surfactant, etc. added to the compound of the present invention are not limited to these examples.

Example 1 Emulsion main compound Meto alkylaryl polyoxyethylene 5 parts dimethylformamide 5 parts xylene
Mix and dissolve 35 parts or more,
Before use, dilute with water and spray as milk ant liquid.

Example 2 Hydrate Ihi compound of the present invention 2 parts Higher alcohol sulfate ester 5 parts Porphyllum ±
7$ parts white carbon Mix 5 parts or more, grind into a fine powder, and dilute with water before use.

Example 3 Powder, compound of the present invention 5 parts talc
94.6 parts silicon
Mix and grind 0.1 part or more of 0.3-mouth alkylaryl polyoxyethylene, and sprinkle as is before use.

Example 4 Granules Compound of the present invention 5 parts Talc
41.75 parts diatoms + 41.75 parts pentonite 1 part sodium ligninsulfonate 1.5 parts or more are mixed to obtain granules.

Next, test examples will be given to explain the insecticidal and mite efficacy of the compound of the present invention.

Test Example 1 Efficacy against Spider mites Thirty female adult spider mites were inoculated onto the first true leaves of green beans planted in a 2-inch pot.

One day later, the injured pests were removed, and the agent of the present invention prepared according to the emulsion formulation shown in the above example was diluted with water to a compound concentration of 500 mg and sprayed.

Three days after spraying, the insecticidal rate was determined and the adults were removed, and the eggs laid during that time were investigated on the 11th day to see if they had developed to adults to determine the degree of acaricidal effectiveness. The results are as follows. *Evaluation of insecticidal rate and acaricidal effectiveness after 3 days: 100%, 80-99%, 50-79%, 0-5
0% (acidicidal effectiveness) = Number of adults completed in the untreated area - Number of completed adults in the treated area X.

〇Number of adults completed in untreated area (Japanese Patent Application Laid-open No. 50-13533) ('') ('') Test Example 2 Efficacy against two-spotted spider mites Discarding of the first green beans 7 to 10 days after germination of green beans sown in 2-inch pots After inoculating 30 female adults of organophosphate-resistant two-spotted spider mites, the drug of the present invention prepared according to the formulation of the emulsion in the above example was applied at a compound concentration of 62. Fu31
．． 3 and 15. It was diluted with water and sprayed on the gun skin.

Three days after spraying, the mite rate was determined, and the adults were removed.The eggs laid during these three days were examined on the 11th day to see if they had developed to adults, and the degree of acaricidal effectiveness was determined. The results are as follows. Evaluation of insecticidal rate after 3 days * Evaluation of crinicidal effectiveness * Compound number 62.5 ppm 31
．． 3ppm 15.6ppm 62.5ppm
31.3ppm 15.6ppml Kawashu W
W square 12 river river 10th 13 M river 14 M river day + 5 state river day + 6 M river river river 17 river state river day day + 8 state MM day 19 state river day 10 11 M river square river day +12 river river 113 M river
Masu 114 River 10 Day 10
115 tithe river day tithe 116
Ji River River River Ji 118 River State River M Day +19 River River
Day +24 State River 10B** -
−C** − ÷ −
One Kelsen river state ten tenths
Days ＋＊, **Evaluation of insecticidal rate after 3 days, evaluation of acaricidal efficacy, and comparative compounds B and C were the same as in Test Example 1.

Test example 3 Efficacy against citrus spider mites Place tangerine leaves on a petri dish, and add 20 female adult citrus spider mites.
Head inoculated.

Tangle was applied around the leaves to prevent adult insects from escaping.
One day later, the agent of the present invention prepared according to the formulation of the emulsion in the above example was diluted with water to a compound concentration of 125 willows and sprayed, and the insecticidal rate was determined three days after spraying.

The results are as follows. Test Example 4 Efficacy against Armyworm The compound of the present invention was diluted with water to a compound concentration of 500% according to the emulsion formulation shown in the above example.

Corn leaves were soaked in the chemical solution for 3 minutes, and after air drying,
The leaves were placed in a petri dish containing five 3rd instar larvae. Close the glass lid, temperature 25q0, humidity 65%
The insecticide rate was examined after 4 hours. The results are as follows. Test Example 5 Efficacy against Houseflies The compound of the present invention was infiltrated to a concentration of 1% into a feed prepared by mixing powdered milk and sugar at a ratio of 1:1.

The bait was placed in a PoIJ ethylene cup containing 20 female adult house flies, water was added, the cup was covered, and the cup was placed in a thermostatic chamber at a temperature of 25°C and humidity of 65%, and the killing rate was examined after 5 days.
The results are as follows. Test Example 6 Efficacy against Chicajeka The compound of the present invention was diluted with water to three parts according to the emulsion formulation shown in the above example.

I put 150 of the chemical solution into a 200' beaker and released 10 3rd instar larvae. The beaker was placed in a thermostatic chamber at a temperature of 25 qC and a humidity of 65% for two repetitions, and the insect killing rate was examined after 7 days.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X_1, X_2 and X_3 are halogen atoms,
Y represents a halogen atom, a lower alkyl group or a lower alkoxy group, n represents 0, 1 or 2, and R_1 and R_2 represent a hydrogen atom, a lower alkyl group, a phenyl group or a benzyl group. ). 2 X_1, X_2 and X_3
The compound according to claim 1, wherein is a bromine atom. 3. The compound according to claim 1 or 2, wherein R_1 and R_2 are lower alkyl groups. 4. The compound according to claim 3, wherein R_1 and R_2 are a methyl group or an ethyl group. 5. The compound according to claim 4, wherein Y is a chlorine atom, a bromine atom, or a methyl group. 6 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X_1, X_2 and X_3 represent halogen atoms with Y
represents a halogen atom, a lower alkyl group or a lower alkoxy group, n represents 0, 1 or 2, R_1 and R_2 represent a hydrogen atom, a lower alkyl group, a phenyl group or a benzyl group. ) An insecticide and acaricide characterized by containing a compound represented by the following as an active ingredient. 7 X_1, X_2 and X_
The insecticide and acaricide according to claim 6, wherein 3 is a bromine atom. 8. The insecticide and acaricide according to claim 6 or 7, wherein R_1 and R_2 are lower alkyl groups. 9. The insecticide and acaricide according to claim 8, wherein R_1 and R_2 are a methyl group or an ethyl group. 10. The insecticide and acaricide according to claim 9, wherein Y is a chlorine atom, a bromine atom, or a methyl group.