RU2032671C1 - Derivatives of 1-phenylimidazole showing insecticide properties and insecticide composition - Google Patents

Abstract

FIELD: agriculture. SUBSTANCE: compound having formula I

Description

N

где R представляет атом водорода или метил;
х представляет атом фтора, атом хлора или нитрогруппу;
y представляет атом фтора или атом хлора;
z представляет атом водорода, атом фтора, атом хлора или атом брома, способу получения этих соединений и инсектицидам, содержащим в качестве активных компонентов эти соединения.The invention relates to new derivatives of 1-phenylimidazole of the formula 1
CF

N

where R represents a hydrogen atom or methyl;
x represents a fluorine atom, a chlorine atom or a nitro group;
y represents a fluorine atom or a chlorine atom;
z represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, a method for producing these compounds and insecticides containing these compounds as active components.

 US Pat. No. 3,868,458, US Pat. No. 3,940,484, and US Pat. No. 3,996,366 indicate that certain imidazole derivatives are useful as active ingredients in insecticides.

 As a result of intensive studies of compounds with excellent insecticidal action, it was found that the derivatives of 1-phenylimidazole of formula 1 exhibit extremely high insecticidal activity, in relation to a wide range of harmful insects both in pure form and in the composition.

 Synthesis example 1 (synthesis of compounds 10).

To a solution of 0.41 (2 mmol) 4 (5) -2- (chloro-1,1,2,2-tetrafluoroethyl) imidazole in 5 ml of N, N-dimethylformamide was added 80 mg (2 mmol) of sodium hydride in oil ( 60%) upon cooling with ice, followed by stirring at the same temperature for 10 minutes. After the reaction, the reaction mixture was added dropwise 0.50 g (2 mmol) of 3,4,5-trihlorbenzoltriftorida followed by stirring for 7 hours at 80-90 ° ^C. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. Then, the residue was washed with brine, dried over magnesium sulfate and concentrated under reduced pressure. The resulting product is chromatographed on silica gel to give 0.23 g of 1- (2,6-dichloro-4-trifluoromethylphenyl) -4- (2-chloro-1,1,2,2-tetrafluoroethyl) imidazole, mp. 101.2 ^about S.

 Synthesis Example 2 (Synthesis of Compound 23)

To a solution of 0.43 g (2 mmol) of 2-methyl-4- (5) - (2-chloro-1,1,2,2-tetrafluoroethyl) imidazole in 5 ml of N, N-dimethylformamide was simultaneously added 0.41 g (3 mmol) of anhydrous potassium carbonate and 0.47 g (2 mmol) of 3,5-dichloro-4-fluorobenzotrifluoride, followed by stirring for 7 hours at 80-90 ^C. The reaction mixture was, after cooling, poured into water, extracted with ethyl acetate, the residue was washed with brine, dried over magnesium sulfate and concentrated under reduced pressure. Chromatography of the product on silica gel afforded 0.33 g of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-methyl-4- (2-chloro-1,1,2,2-tetrafluoroethyl) imidazole, m.p. 134.3 ^about S.

 Examples of compounds of the invention synthesized by the above procedure are shown in table 1.

 The following are examples of formulations where all parts are given by weight, and the compounds of the present invention are indicated by the numbers indicated in table 1.

 Formulation Example 1. Emulsifiable concentrate.

 After 10 parts of each of the compounds (1) to (27) of the invention have been dissolved in 35 parts of xylene and 35 parts of dimethylformamide, 14 parts of styrylphenyl ether of polyoxyethylene and 6 parts of calcium dodecylbenzenesulfonate are added to the solution. The resulting mixtures are thoroughly mixed and as a result receive a 10% emulsifiable concentrate.

 Formulation Example 2. Wettable Powder.

 After adding 20 parts of compound 1-27 of the invention to a mixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium lignosulfonate, 20 parts of fine synthetic hydrated silicon dioxide powder and 54 parts of diatomaceous earth, the mixture is stirred in a juice mixer and 20% are obtained - wettable powder.

 An example of the composition 3. Granules.

 After adding 5 parts of a fine powder of synthetic hydrated silicon dioxide, 5 parts of dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay to 5 parts of the compound (1) to (27) of the invention, the mixture is thoroughly mixed. After stirring, the required amount of water is added to the mixture. The mixture is granulated with a granulator and, after drying in air, 5% granules are obtained.

 Examples of the composition 4. Dust.

 After 1 part of compound 22 of the invention has been dissolved in an appropriate amount of acetone, 5 parts of a fine synthetic hydrated silica powder, 0.3 parts of PAP and 93.7 parts of clay are added to the solution. The mixture is stirred in a juice mixer and after evaporation of acetone get 1% dust.

 An example of the composition 5. Loose concentrate.

 After mixing 20 parts of compound 23 of the invention and 1.5 parts of trioleate with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, the mixture is finely ground (to particles with a diameter of less than 3 μm, using a sand eraser. Then to the powder 40 parts of an aqueous solution containing 0.05 parts of xanthan gum and 0.1 parts of aluminum-magnesium silicate are added, and 10 parts of propylene glycol are added, the mixture is thoroughly mixed and a 20% free-flowing concentrate for aqueous suspensions is obtained.

 An example of the composition 6. Oil spray.

 After dissolving the compound 1-27 of the invention (0.1 parts) in 5 parts of xylene and 5 parts of trichloroethane, the solution is mixed with 89.9 parts of deodorized kerosene and 0.1% oil spray is obtained.

 Formulation Example 7. Oil-based aerosol.

 0.1 parts of compound 1-27 of the invention, 0.2 parts of tetramethrin, 0.1 parts of d-phenotrin, 10 parts of trichloroethane and 59.6 parts of deodorized kerosene are mixed and dissolved, and aerosol containers are filled with the resulting solution. After the valve is installed under pressure, 30 parts of propylene (liquefied petroleum gas) are pumped through the valve and an oil-based aerosol is obtained.

 An example of the composition 8. Water spray.

 Mix with each other and dissolve 0.2 parts of compound 24 of the invention, 0.2 parts of d-allethrin, 0.2 parts of d-phenotrin, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of emulsifier [ATMOS 300 (registered trademark, AtLaS Chemical Co. Ltd.)] and the resulting solution, together with 50 parts of distilled water, fill the aerosol container. After the valve is installed on the container, 40 parts of the propellant (liquefied petroleum gas) are pumped under pressure through it to obtain an aqueous aerosol.

 An example of the composition 9. Mosquito spiral.

 After adding 0.3 parts of d-allethrin to 0.3 g of compound 20 of the invention, the mixture was dissolved in 20 ml of acetone. The solution is then uniformly mixed with 99.4 g of a mosquito coil carrier (tobacco powder: seiksil powder, wood flour 4: 3: 3) with stirring, after which 120 ml of water are added to the mixture. The mixture is thoroughly kneaded, molded and, after drying, a mosquito coil is obtained.

 An example of the composition 10. Electric mosquito mat.

 A mixture of 0.4 g of compound 19 of the invention, 0.4 g of o-allethrin and 0.4 g of piperonyl butoxide is dissolved in acetone to a hollow volume of 10 ml. The resulting solution (0.5 ml) is uniformly impregnated with the base material (a mixture of cotton fluff and pulp cured in the form of a plate) of an electric mat 2.5x1.5 cm in size and 0.3 cm thick to obtain an electric mosquito mat.

 An example of the composition 11. Fumigant.

 After dissolving 100 ml of the compound 16 of the invention in the required amount of acetone, the resulting solution is impregnated with a porous ceramic plate 4x4 cm in size and 1.2 cm thick to obtain a fumigant.

 An example of the composition 12. Poisoned bait.

 After dissolving 10 mg of compound 1-27 of the invention in 0.5 ml of acetone, the resulting solution is applied to 5 g of dry food, powdered. After drying the powder, a 5% poison bait is obtained.

 An example of the composition 13. Oil solution.

 95 parts of each of compounds 6 or 12 of the invention were mixed with 5 parts of purified kerosene to obtain a 95% oil solution.

 Further, the effectiveness of the compounds of the invention as active components of insecticidal compositions is described with reference to test examples, where the compounds of the invention are indicated by the numbers given in table 1, and the compounds used for comparison and control are indicated by the numbers given in table 2.

 Test Example 1 (insecticidal test on brown plant flea nymphs).

The emulsifiable concentrate of the test compound prepared in accordance with Example 1 is diluted with water (respectively to a concentration of 500.5 or 0.5 ppm) and rice plant sprouts (about 12 cm long) are immersed in the diluted solution for a minute. After air drying, the rice plant sprouts are placed in a test tube, where about 30 nymphs of a brown plant flea (Nilaparvata Lugens) are also placed. Six days later, the presence of living and dead nymphs is revealed. Test assessment is indicated as follows:
and the absence of live insects
b live insects 5 or less
from live insects 6 or more
The results are shown in table.3.

 Test Example 2 (insecticidal test on the long-billed southern flea)

At the bottom of a polyethylene cup with a diameter of 5.5 cm, filter paper of the same size was placed onto which 1 ml of an aqueous diluted (500 or 50 ppm) emulsifiable concentrate of the test compound prepared in accordance with Example 1 was placed and placed on it as food one sprout of corn. Approximately 30 eggs of the southern long-nosed flea (Diabrotica undecumpynotata) are placed in a cup. Eight days after covering the cup, the presence of live or dead hatching larvae is detected. The test result criterion is as follows:
a lack of live insects
b live insects 5 or less
from live insects 6 or more
The results are shown in table 4.

 Test examples 3 (insecticidal test on the long-billed southern flea)

 5 ml of a diluted aqueous emulsifiable concentrate of the test compound obtained in accordance with example composition 1, is mixed with 50 g of sifted (16 mesh) soil. The concentration of the active component in the soil is set to 0.25 or 0.125 ppm.

 Each soil sample is introduced into a polyethylene cup with a diameter of 5.6 cm and a height of 5.8 cm, in which two maize seeds with 2-3 cm long roots are sown. Then 10 larvae of the long-barked southern flea (Diabrotica undecimpunctata howardi) in the third larva are released stage. Two days later, the number of treated insects (dead or agonizing) and non-treated insects (energetic) was counted, revealing the effectiveness (%) of the compounds. The results are shown in table 5.

 Test Example 4 (insecticidal test on an ordinary mosquito).

 The emulsifiable concentrate of the test compound obtained in accordance with Example 1 was diluted with water and a diluted solution (0.7 ml) was added to 100 ml of deionized water (active component concentration 3.5 ppm). 20 larvae of the common mosquito (Culex pipiens pallens) in the last larval stage are released into the mixture. One day after release, mortality among the larvae is detected.

Evaluation criteria are indicated as follows:
90% or higher
b not less than 10% but less than 90%
with at least 10%
The results are shown in table.6.

 Test Example 5 (Insecticidal Test on Prusaks).

 At the bottom of a polyethylene cup with a diameter of 5.5 cm, filter paper of the same size is placed onto which 0.7 ml of an aqueous diluted (500 ppm) emulsifiable concentrate of the test compound is prepared, prepared in accordance with Example 1. As food on filter paper evenly distribute 30 mg of sucrose. 10 adult male red cockroaches (Prussians) (Blattella germanica) are launched into the cup. Six days after covering the plates, the number of dead and living insects is determined to calculate mortality.

 The results are shown in table.7.

 Test Example 6 (insecticidal test on a housefly).

 At the bottom of a polyethylene cup with a diameter of 5.5 cm, filter paper of the same size is placed onto which 0.7 ml of an aqueous diluted (500 ppm) emulsifiable concentrate of the test compound is prepared, prepared in accordance with Example 1. As food on filter paper evenly distribute 30 mg of sucrose. 10 adult female domestic flies (Mysca domestica) are launched into the cup. 48 hours after covering the plate, the number of dead or living insects is determined with mortality (2 repetitions). The results are shown in table.8.

Claims (2)

1. Derivatives of 1-phenylamidazole of the General formula

where R is hydrogen, methyl;
X fluorine, chlorine, nitro group;
y fluorine, chlorine;
Z is hydrogen, fluoro, chloro or bromo,
exhibiting insecticidal properties. 2. Insecticidal composition containing a derivative of 1-phenylimidazole and target additives, characterized in that as a derivative of 1-phenylimidazole use a compound of the General formula

where R is hydrogen, methyl;
X fluorine, chlorine, nitro group;
y fluorine, chlorine;
Z is hydrogen, fluoro, chloro or bromo,
in an amount of 0.1 to 95.0 wt. targeted additives rest.

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