JPH0369338B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides novel substituted N-benzoyl-N'-
The present invention relates to a 2,5-dihalo-4-haloalkoxyphenylurea, a method for producing the same, and an insecticide and acaricide containing the compound. The compound of the present invention has the following formula: (In the formula, each of R ₁ and R ₂ represents a halogen atom, but R ₁ and R ₂ do not represent a chlorine atom at the same time, R ₃ represents -CF ₂ -CHF-CF ₃ , and R ₄
represents a hydrogen atom, a halogen atom, a methyl group, a methoxy group or a methylthio group, and R ₅ represents a halogen atom, a methyl group, a methoxy group or a methylthio group. ) is a compound represented by Suitable halogen substituents are fluorine, chlorine, bromine and iodine;
Chlorine and bromine atoms are preferred. Of particular interest are compounds represented by the formula in which each of R ₁ and R ₂ represents a fluorine atom, a chlorine atom or a bromine atom, provided that R ₁ and R ₂ do not simultaneously represent a chlorine atom, and R ₃ is - _CF2 −CHF
_-CF3 , _R4 represents a hydrogen atom, a fluorine atom or a chlorine atom, and _R5 represents a fluorine atom, a chlorine atom or a methoxy group. Preferred compounds of the formula are:
R ₁ represents a fluorine atom, and R ₂ represents a fluorine atom,
represents a chlorine atom or a bromine atom, or R ₁
represents a chlorine atom, _R2 represents a fluorine atom, _R3 represents _-CF2CHF - _CF3 , _R4 represents a hydrogen atom, a fluorine atom or a chlorine atom, and
R ₅ represents a fluorine atom, a chlorine atom or a methoxy group. The compounds of the present invention can be produced by known methods. Such methods are described inter alia in DE 2123236, DE 2601780 and DE 3240975. Such a compound represented by the formula may be, for example, (a): The aniline expressed by the following formula: or (b) with a benzoyl isocyanate of the following formula: The isocyanate represented by the following formula: or react with a benzamide represented by (c) the aniline represented by the formula: (In the above formulas, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meaning as defined in the formula, and R is the number of carbon atoms that may be substituted with a halogen atom, preferably a chlorine atom. (representing 1 to 8 alkyl groups). The above methods (a), (b) and (c) can preferably be carried out under normal pressure and in the presence of an organic solvent or diluent. Examples of suitable solvents or diluents are: ethers and ether-like compounds such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylated carboxamides; aliphatic, aromatic and halogens. hydrocarbons, especially benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride, and chlorobenzene; nitriles such as acetonitrile or propionitrile; dimethyl sulfoxide; and ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone. be. (a) Normally -10° to +
It is carried out at 200°C, preferably from 0° to 100°C, for example at room temperature, and if desired in the presence of an organic base such as trimethylamine. (b) The temperature is 0℃ or
It is carried out at 150 DEG C., preferably at the boiling point of the solvent used, optionally in the presence of an organic base such as pyridine and/or with the addition of an alkali or alkaline earth metal, preferably sodium.
(c), i.e., about 60°C for the reaction of the urethane with the aniline of the formula
to the boiling point of the reaction mixture is preferred, and the solvents used are preferably aromatic hydrocarbons such as toluene, xylene, chlorobenzene and the like. The starting materials of the formula and are known and can be prepared by methods analogous to known methods. The starting material of the formula is a new compound. The compound represented by the formula is the following formula, appropriately substituted by a known method: of nitrobenzene was converted to hydrogen by a method analogous to that described in Journal of Organic Chemistry (J.Org.Chem.), Vol. 29 (1964), 1 (see also references cited herein). It can be manufactured by converting into However, the anilines of the formula can also be obtained by chemical reduction (for example with stannous chloride/HCl) of the corresponding nitro compounds of the formula. [Houben-Weyl, “Methoden d.org.Chemie”
11/1, 422]. Another method for preparing anilines of the formula is unacylated or acylated 2,5-
It consists of haloalkylating the dihalo-4-hydroxyaniline and then, if appropriate, removing the acyl group, for example by acid hydrolysis. The nitro compounds of the formula are also new.
These compounds include, for example, 2,5-dihalo-4-
By haloalkylating nitrophenols (see FR 2005876) or by reacting 2,5-dihalo-4-fluoronitrobenzenes with haloalkanols in alkaline solution and dimethyl sulfoxide as solvent [“ Chemistry of hydroxyl groups (The
Chemistry of the Hydroxyl Group)” pages 83-124; Interscience
Publications, New York, 1971] can be manufactured. The benzoyl isocyanate of the formula can in particular be obtained as follows [see Journal of Agricultural Food Chem., Vol. 21, pp. 348 and 993; 1973] : The 4-haloalkoxyphenyl isocyanate represented by the formula can be produced, for example, by phosgenating the aniline represented by the formula by a method commonly used in the art. The benzamides of the formula used as further starting materials are known (for example, in Beilstein's "Handbuch der Organitsien Chemie").
Urethane represented by the formula can be obtained by reacting benzoyl isocyanate represented by the formula with an appropriate alcohol by a method known per se.
Alternatively, the benzamide represented by the formula can be converted into the corresponding ester of chloroformic acid Cl− in the presence of a base.
It can be obtained by reacting with COOR. It has surprisingly been found that the compounds of the invention are excellent pest control agents and at the same time are well tolerated by mixed-breed animals and plants. The compounds of the formula are therefore suitable for example for the control of animal and plant pests. Such pests mainly belong to the phyla Arthropoda, such as Lepidoptera, Coleoptera, Homoptera, Heteroptera, Dipteta, Thrips, among others. Order (Thysanoptera), Order (Orthoptera), Order (Anoplura), Order (siphonaptera), Order (Mallophaga),
Thysanura, Isoptera,
Insects of the order Psocoptera, or Hymenoptera, and arachnids of the order Acarina, such as mites
and ticks. It is possible to control all developmental stages of the pest, ie adults, pupae and nymphs, and especially larvae and eggs. In this way, it is possible to effectively control phytopathogenic insect pests and especially larvae and eggs of mites in ornamental and useful plants, such as fruit and vegetable crops and especially in cotton crops. When compounds of the formula are ingested by adult insects, direct death of pests or a reduction in egg production and/or hatchability is observed. The last mentioned effectiveness is especially observed in Coleoptera. In the control of pests that are parasites of animals, in particular livestock and productive livestock, the compounds of the invention are particularly suitable against ectoparasites such as ticks and ticks and against polypterans such as Lucilia sericata. be. A good pest control action of the compounds of the formula according to the invention corresponds to a mortality rate of at least 50-60% of the abovementioned pests. The action of the compounds of the formula and compositions containing them can be substantially extended and adapted to the application environment by adding other insecticides and/or acaricides. Examples of suitable additives include organic scale compounds, nitrophenols and their derivatives, formamide,
Contains urea, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations. In its natural form, the compound represented by the formula
or emulsion concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, aqueous solutions, powders, granules and capsules of e.g. polymeric substances, preferably with the auxiliaries customary in formulation technology, by known methods. It is formulated into a chemical agent. As well as the nature of the composition, spraying, atomizing, dusting,
The application method, such as sprinkling or pouring, is chosen depending on the intended target and the environment of use. Preparations, i.e. compositions, preparations or mixtures containing the compound of the formula (active principle) or its combination with other insecticides or acaricides and, where appropriate, solid or liquid auxiliaries, are known in the art. They are prepared, for example, by homogeneous mixing and/or milling of the active ingredient with fillers, such as solvents, solid carriers and, in some cases, surface-active compounds (surfactants). Suitable solvents are: aromatic hydrocarbons, preferably C8 -C12 moieties, such as xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffin, Alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide and vegetable oils or epoxidized vegetable oils such as epoxidized coconut oil or soybean oil;
Or water. The solid carriers used, for example in powders and dispersible powders, are usually natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. It is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers to improve the physical properties. Suitable granulated absorbent carriers are of porous type, for example pumice, crushed brick, sepiolite or bentonite; and suitable non-absorbent carriers are materials such as calcite or sand. Furthermore, a large number of pre-granulated mineral and organic materials can be used, such as in particular dolomite or granulated plant debris. Depending on the nature of the compound to be formulated or its combination with other insecticides or acaricides, suitable surface-active compounds include non-ionic, cationic compounds with good emulsifying, dispersing and wetting properties. and/or an anionic surfactant. It is to be understood that the term "surfactant" also includes mixtures of surfactants. Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds. Suitable soaps are higher fatty acids (10 carbon atoms or less)
alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of 22), such as oleic acid or stearic acid, or the sodium or potassium salts of natural fatty acid mixtures obtained, for example, from coconut oil or tallow. Other suitable surfactants are also fatty acid methyltaurate salts and modified and unmodified phospholipids. However, more frequently so-called synthetic surfactants are used, especially aliphatic sulfonates, aliphatic sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. The aliphatic sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain C8-C22 alkyl groups, which also include the alkyl part of the acyl group; For example, the sodium or calcium salts of lignosulfonic acid, dodecyl sulfate or mixtures of fatty alcohol sulfates obtained from natural fatty acids.
These compounds also include salts of sulfuric acid esters and salts of sulfonic acids of aliphatic alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty acid group containing from 8 to 22 carbon atoms. Examples of alkylaryl sulfonates are:
Sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid/formaldehyde condensation products. Also suitable are the corresponding phosphates, for example salts of the phosphoric esters of p-nonylphenol adducts containing 4 to 14 mol of ethylene oxide. The non-ionic surfactants are preferably aliphatic or cycloaliphatic alcohols or polyglycol ether derivatives of saturated or unsaturated fatty acids and alkyl phenols, which derivatives contain 3 to 30
glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon portion and 6 to 18 carbon atoms in the alkyl portion of the alkylphenol. Other suitable nonionic surfactants are water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycols containing 1 to 10 carbon atoms in the alkyl chain; The product contains 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Typical examples of nonionic surfactants are nonylphenol polyethoxyethanol, castor oil polyglycol ether, castor oil thioxylate, polypropylene/polyethylene oxide adduct, tributylphenol polyethoxyethanol, polyethylene glycol, and octylphenol. It is ethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan triolate, are also suitable nonionic surfactants. Cationic surfactants preferably contain at least one carbon atom as N-substituent.
and an unsubstituted or halogenated lower alkyl group, benzyl group or lower hydroxyalkyl group as other substituents. The salt is preferably in the form of a halide, methyl sulfate or ethyl sulfate, such as stearyltrimethylammonium chloride or benzyldi-(2-chloroethyl)ethylammonium bromide. Surfactants customary in the pharmaceutical industry are described, for example, in the following publication: “Mc Cutcheon's Detergents and Emulsifiers Annual.
Emulsifiers Annual)”, Matsuku Publishers, Ltd., New Jersey, 1979; Dr. Helmut
Stache), “Tensid Tashenbuch”, Carl Hanser Verlag, Millenchen and Vienna (1981). Pest control compositions usually contain from 0.1 to 99%, preferably from 0.1 to 95%, of a compound of the formula or a combination thereof with other insecticides or acaricides, and from 1 to 99.9% of a solid or liquid adjuvant.
%, and surfactant 0 to 25%, preferably
Contains 0.1 to 25%. Although commercial products are preferably formulated as concentrates, consumers typically use dilute formulations with substantially lower concentrations. The composition may also contain other additives, such as stabilizers,
Antifoams, viscosity regulators, binders, tackifiers as well as fertilizers or other active ingredients may be included to obtain special effects. Examples Example 1 Preparation 1.1.2.6 2-Fluoro-(4-1,1,2,3,
3,3-Hexafluoropropoxy)-5-bromoaniline 28 g of 2-bromo-4-amino-5-fluorophenol and 1.9 ml of triethylamine are placed in 150 ml of dimethylformamide. 22.5 g of hexafluoropropylene are then introduced at room temperature and the temperature of the batch rises to 50°C. Subsequently, the solvent is distilled off in vacuo, the residue is taken up in ether and the ethereal solution is extracted twice with dilute sodium hydroxide solution and twice with water. The ethereal extract was dried over sodium sulfate and then subjected to fractional distillation, giving the following formula: The title compound is obtained in the form of a pale yellow liquid: boiling point 76-81°C/0.001 torr. The following compounds were prepared in a similar manner:

[Table] 1.2 Final product 1.2.1 N-(2,6-difluorobenzoyl)-
N'-[2-fluoro-4-(2,2,2-trifluoroethoxy)-5-chlorophenyl]
Urea (reference example) A solution of 3.0 g of 2,6-difluorobenzoyl isocyanate in 10 ml of dry toluene,
2-Fluoro-4- in 50 ml of dry toluene
(2,2,2-trifluoroethoxy)-5-
Added to a solution of 4 g of chloroaniline at room temperature,
The batch is then stirred for 10 hours. Approximately 75% of the solvent is subsequently removed by rotary evaporation. The precipitate formed was separated by suction filtration, washed with a small amount of cold toluene and hexane, and dried under vacuum, following the formula: The title compound is obtained in the form of a white crystalline powder; mp 201-202°C. 1.2.2 The following compounds were produced according to the method of 1.2.1. above.

【table】

[Table] 1.2.3 N-(2,6-difluorobenzoyl)-
N′-[2,5-difluoro-4-(1,1,
2,3,3,3,-hexafluoropropoxy)-phenyl]-urea 20 dissolved in toluene in a reaction flask.
Add 135 ml of % solution phosgene. Add 200 ml of dioxane to the solution and heat to 65°C. While maintaining this temperature, 22.0 g of 2,5-difluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-aniline is added dropwise. The reaction mixture is stirred first at 60°C for 1 hour and then at 100°C for 4 hours. the solvent mixture at a pressure of less than 130 mbar,
and fractional distillation at a temperature of 48°C. The residue is fractionated under high vacuum. 2,5-difluoro-4-(1,1,2,3,3,3-
18.0 g of (hexafluoropropoxy)-phenyl isocyanate are obtained. 7.85g of 2,6-
Difluorobenzamide, 16.0 g of 2,5-
difluoro-4-(1,1,2,3,3,3
-Hexafluoropropoxy)-phenyl isocyanate and 150 ml of xylene are stirred at a temperature of 130° C. for 10 hours. The solvent is fractionally distilled off and the residue of the mixture is crystallized from toluene and hexane. By this method, the following formula: N-(2,6-difluoro-benzoyl)-N′-[2,5-difluoro-4
-(1,1,2,3,3-hexafluoropropoxy)-phenyl]-urea is obtained. Analysis: C ₁₇ H ₈ F ₁₀ N ₂ O ₃ Calculated values: C42.70% H1.69% N5.86% F39.73% Experimental values: C42.80% H1.60% N6.00% F39.50% Example 2 Formulation example of the active ingredient represented by the formula according to Production Example 1.2 (% is % by weight throughout) 2.1 Emulsion stock solution

【table】

[Table] By diluting this emulsion stock solution with water, an emulsion of a desired concentration can be obtained. 2.2 Solution

[Table] These solutions are suitable for application in the form of microdroplets. 2.3 Granules (a) (b) Compound according to Preparation Example 1.2 5% 10% Kaolin 94% - Highly dispersed silicic acid 1% - Attapulgite - 90% The active ingredient is dissolved in methylene chloride and this solution is sprayed onto the carrier, Subsequently, the solvent is distilled off under reduced pressure. 2.4 Preparation of Extruded Granules Compound according to Example 1.2 10% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 87% The active ingredients are mixed and milled together with the auxiliaries and the mixture is subsequently moistened with water. The mixture is extruded and dried in a stream of air. 2.5 Coated Granule Preparation Compound according to Example 1.2 3% Polyethylene Glycol 200 3% Kaolin 94% The finely ground active ingredient or formulation is applied uniformly to the kaolin moistened with polyethylene glycol in a mixer. This method provides dust-free coated granules. 2.6 Powders

By mixing the active ingredient with the carrier and milling the mixture in a suitable mill, a ready-to-use powder is obtained. 2.7. Hydrating agents

[Table] Sodium phonate

[Table] After thoroughly mixing the active ingredient with the auxiliaries, the mixture is thoroughly ground in a suitable mill. A wettable powder is obtained which can be diluted with water to obtain a suspension of the desired concentration. 2.8 Suspending agent stock solution Compound according to Preparation Example 1.2 40% Ethylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6% Sodium lignosulfonate 10% Carboxymethyl cellulose 1% 37% formaldehyde aqueous solution 0.2% 75% aqueous emulsion form silicone oil
0.8% Water 32% A suspendable concentrate is obtained by uniformly mixing the finely ground active ingredient with auxiliaries and diluting with water to obtain a suspension of the desired concentration. Example 3 Biological test 3.1 Effect on house fly (Musca domestica) Fill a beaker with 50 g of freshly prepared CSMA nutrient medium against maggots. 1 test compound
Pipette 5 ml of the acetone solution containing % by weight into the nutrient medium in the beaker. The acetone is then allowed to evaporate for at least 20 hours after the medium has been thoroughly mixed. Twenty-five one-day-old housefly maggots are then placed in a beaker containing the treated nutrient medium. After the maggots have pupated, separate the pupae by flushing them out of the medium with water and place them in a container closed with a perforated lid. Each batch of flushed pupae is counted to determine the toxic effect of the test compound on maggot development. Measurements are made by counting the number of flies that have transformed from pupae to adults after 10 days. In this test the compound according to Example 1.2 showed a good effect. 3.2 Lucilia sericata
Effect on 1 ml of aqueous formulation containing 0.5% test compound
is added to 9 ml of nutrient medium at 50°C. after that,
Insecticidal activity is investigated by adding approximately 30 newly hatched Lucilia cercata larvae to the nutrient medium and assessing mortality after 48 and 96 hours. In this test, the compound according to Example 1.2 showed good action against Lucilia cercata. 3.3 Action against the Egyptian aegypti mosquito (Ae¨des aegypti) On the surface of 150 ml of water in a beaker, pipet an aliquot of a 0.1% acetone solution of the test compound to obtain a solution with a concentration of 12.5 ppm. Two-day-old Egyptian Aedes mosquito larva after acetone evaporates.
Place 30 to 40 animals in a beaker containing the test compound. Count the number of dead insects after 2 and 7 days. In this test the compound according to Example 1.2 showed a good effect. 3.4 Insecticidal action against feeding insects Cotton plants (approximately 20 cm in height) are each sprayed with an aqueous emulsion (prepared from a 10% emulsion stock solution) containing the test compound at a concentration of 100 ppm. After the spray coating has dried, Spodoptera littoralis and Heliothis
Populate cotton plants with L ₃ stage larvae of Heliothis virescens. The test was conducted at 24℃.
Perform at 60% relative humidity. After 24 hours, count the number of dead insects and check for inhibition of larval development and molting. In this test the compound according to Example 1.2 showed a good effect. 3.5 Effect on Spodoptera littoralis and Heliothis viretscens (larvae and eggs) Three cotton plants, grown in pots and having a height of approximately 15 to 20 cm, are each treated with a sprayable liquid formulation of the test compound. After the spray coating has dried, the potted plants are placed in a metal container with a capacity of about 20 ml and covered with a glass plate. The humidity in the covered container is adjusted so that no condensed water forms. Avoid direct light hitting the plant. All three straight bodies then had: (a) 50 L ₁ stage larvae of Spodoptera ritstoralis or Heliothis viretscens; (b) 20 L ₃ stage larvae of Spodoptera ritstoralis or Heliothis viretscens; (c) Spodoptera ritstoralis or Heliotis viretscens. Infect with two deposits of Viretscens eggs. (The procedure is to place two leaves from each plant into a Plexiglas cylinder with steel closed at both ends.) Two deposits of Spodoptera eggs;
Or add some of the cotton leaves on which Heliothis eggs have accumulated to the leaves sealed in the cylinder. ) Rating of 4 to 5 compared to untreated control
After several days, the test was carried out according to the following criteria. (a) Number of larvae still alive (b) Inhibition of larval development and pupation (c) Feeding damage (breakage and puncture damage) (d) Hatching rate (number of larvae hatched from eggs) In this test, The compound according to Example 1.2 is
Shows good annihilation effect at a concentration of 400ppm. 3.6 Ovicidal action against Spodoptera littoralis Eggs of Spodoptera littoralis accumulated on paper were cut together with the paper, and then 0.05% by weight of each test compound in a 1:1 mixture of acetone and water.
Immerse in solution. The treated pile is then removed from this mixture and kept in a plastic dish at 28° C. and 60% humidity. Hatching rate, ie the number of larvae developed from treated eggs, was determined after 5 days. The compound according to Example 1.2 showed good efficacy in this test. 3.7 Laspeyresia Pomonera
Pommonella) (eggs) A deposit of Las Peiresia Pomonella eggs within 24 hours after spawning is immersed on paper for 1 minute in an acetone solution containing 400 ppm of the test compound. After the solution dries, place the eggs in a Petri dish and incubate for 28
Keep at temperature of °C. After 6 days, the percentage of larvae hatched from treated eggs is determined. The compound according to Example 1.2 showed good efficacy in this test. 3.8 Effects on reproduction of Anthonomous grandis Adults of Anthonomous grandis within 24 hours of hatching are transferred in groups of 25 into closed cages. This cage is then placed in an acetone solution containing 0.1% by weight of the test compound for 5 to 10 minutes.
Soak for seconds. Once the beetles are dry, they are placed in a covered dish containing food and left to mate and lay eggs. Egg deposits are flushed out under running water two or three times a week, counted, sterilized by placing in an aqueous disinfectant for 2 to 3 hours, and then placed in a dish containing appropriate larval food. Count the number of larvae after 7 days to determine if the larvae have hatched from the eggs. The persistence of the reproductive inhibitory effect of the test compound is determined by examining egg deposits over a period of about 4 weeks. The evaluation is carried out by the reduction in the number of eggs and hatched larvae compared to the untreated control group. In this test, the compound according to Example 1.2 was
Shows good reproductive suppression effect. 3.9 Effect on Anthonomus grandis (adult) Two six-leaf stage and cotton plants in pots are sprayed with a hydratable emulsion containing the test compound at a concentration of 100 ppm. After the sprayed coating has dried (approximately 1 1/2 hours), each plant is infested with beetles (Anthonomas
10 adult insects (G. grandis) live there. A plastic cylinder with a screen on top is immediately placed over the treated plant containing the insects to prevent the beetles from moving from the plant. 25 treated plants
℃ and 60% relative humidity. The evaluation is carried out after 2, 3, 4 and 5 days by examining the beetle mortality rate (percent dorsal) and the anti-feeding effect compared to the untreated control group. In this test the compound according to Example 1.2 showed good efficacy. 3.10 Mexican broad bean weevil (Epilachna)
Effect on Phaseolus vulgaris plants (dwarf bean: 15 to 20 cm high)
dwarf beans) are sprayed with an aqueous emulsion of the test compound at a concentration of 800 ppm. After the sprayed coating dries, the Mexican broad bean weevil (Mexican broad bean weevil)
Inhabit each plant with 5 larvae of L ₄ stage of beanbeetle. Immediately cover the treated plants with a plastic cylinder and top with a copper screen.
The test is conducted at 28°C and 60% relative humidity. 2
And examine the mortality rate after 3 days. Insects in this test are observed for an additional 3 days to evaluate feeding damage (antiphagy) and inhibition of growth and molting. In this test the compound according to Example 1.2 showed a good effect. 3.11 Ovicidal action against Heliotis viretscens and Spodoptera littoralis A corresponding amount of the wettable powder containing 25% by weight of the test compound is mixed with a sufficient amount of water to produce an aqueous emulsion with an active ingredient concentration of 400 ppm.
Deposit of 1 day old eggs of Heliothis on cellophane and 1 day old eggs of Spodoptera on paper
Immerse in these emulsions for a minute and then collect by suction in a circular strainer. Place the treated heap in a Petri dish and keep at 28°C and 60% relative humidity in the dark. Hatching rate, ie the number of larvae hatched from treated eggs, is determined after 5 to 8 days compared to untreated controls. The compound according to Example 1.2 was tested in this test.
Shows an ovicidal effect (mortality rate) of 80 to 100%. 3.12 Effect on Las Peiresia Pomonella (eggs) A deposit of Las Peiresia Pomonella eggs within 24 hours after spawning is immersed on paper for 1 minute in an acetone solution containing 800 ppm of the test compound. After the solution dries, place the eggs in a Petri dish and incubate for 28
Keep at temperature of °C. After 6 days, the percentage of larvae hatched from treated eggs and the mortality rate are determined. The compound according to Example 1.2 shows good efficacy in this test. Comparative test example () Test compound () Control compound A N-(2,6-difluorobenzoyl)-
N'-[2,5-dichloro-4-(1,1,2,
2-tetrafluoroethoxy)-phenyl]-
Urea Compounds described in Example 1(B) in column 2 and the table in column 6 of US Pat. No. 4,518,804. () Compound 1.2.11 (compound of the invention) N-(2,6-difluorobenzoyl)-
N′-[2,5-difluoro-4-(1,1,
2,3,3,3-hexafluoropropoxy)-phenyl]-urea () Compound 1.2.19 (Compound of the invention) N-(2,6-difluorobenzoyl)-
N'-[5-bromo-2-fluoro-4-(1,
1,2,3,3,3-hexafluoropropoxy)-phenyl]-urea () Compound 1.2.24 (Compound of the invention) N-(2,6-difluorobenzoyl)-
N'-[5-chloro-2-fluoro-4-(1,
1,2,3,3,3-hexafluoropropoxy)-phenyl]-urea A 5% emulsion stock solution of the above active ingredient was prepared,
The stock solution is diluted with water to the application concentration. () Insecticidal activity against Spodoptera littoralis and Heliothis viretscens Potted soybean plants grown in a greenhouse up to the 4th to 5th leaf stage were sprayed with an aqueous dispersion of the test compound at the application concentration shown in the table below. thoroughly moisten the plants. After drying, the leaves are cut and placed on moist filter paper in a Petri dish and populated with 40 L1 stage larvae of Spodoptera littoralis or 20 L1 stage larvae of Heliothis viretscens. During the entire test period, the temperature was maintained at 25° C., relative humidity was 55%, and dim light was maintained. Test evaluations were conducted 6 days after inhabitation. Larva mortality rate (%)
was determined relative to untreated controls. The results are shown in the table below.

[Table] () Conclusion It is necessary to achieve a mortality rate of at least 80% in order to successfully control the pests being treated. This requirement is achieved for control compound A only at the highest concentrations in each of the above tests (0.8 ppm for Spodoptera littoralis and 3 ppm for Heliothis viretscens). In contrast, in the case of the compounds of the present invention, the concentrations of control compound A are as low as 25-50% of the required amount (0.2-0.4 ppm for Spodoptera littoralis;
0.8 to Heliothis viretscens
1.5ppm), the above requirements are achieved. Thus, the compounds of the present invention allow for a drastic reduction in the application rate of the active ingredient compared to the prior art compounds, and such an effect is completely unexpected.

Claims (1)

[Claims] Primary formula: (In the formula, each of R ₁ and R ₂ represents a halogen atom, but R ₁ and R ₂ do not represent a chlorine atom at the same time, R ₃ represents −CF ₂ −CHF−CF ₃ , and R ₄ represents a hydrogen atom, a halogen atom, a methyl group, a methoxy group, or a methylthio group, and R ₅ represents a halogen atom, a methyl group, a methoxy group, or a methylthio group. 2 In the above formula, each of R ₁ and R ₂ is a fluorine atom,
Represents a chlorine atom or a bromine atom, provided that R ₁ and R ₂ do not represent a chlorine atom at the same time, and R ₃ represents −CF ₂
The compound according to claim 1, which represents -CHF- _CF3 , _R4 represents a hydrogen atom, a fluorine atom, or a chlorine atom, and _R5 represents a fluorine atom, a chlorine atom, or a methoxy group. 3 In the above formula, R ₁ represents a fluorine atom, and R ₂ represents a fluorine atom, a chlorine atom, or a bromine atom, or R ₁ represents a chlorine atom, and R ₂
represents a fluorine atom, R ₃ represents −CF ₂ −CHF−CF ₃ , R ₄ represents a hydrogen atom, a fluorine atom, or a chlorine atom, and
The compound according to claim 2, wherein R ₅ represents a fluorine atom, a chlorine atom, or a methoxy group. 4 In the above formula, R ₁ represents a fluorine atom, R ₂ represents a fluorine atom, a chlorine atom, or a bromine atom, R ₃ represents -CF ₂ -CHF-CF ₃ , and R ₄ represents a hydrogen atom or a fluorine atom. The compound according to claim 3, wherein R ₅ represents a fluorine atom, a chlorine atom, or a methoxy group. 5th order formula: The compound according to claim 1, which is represented by: Sixth formula: The compound according to claim 1, which is represented by: 7 Formula: The compound according to claim 1, which is represented by: 8th formula: The compound according to claim 1, which is represented by: 9 Formula: The compound according to claim 1, which is represented by: 10th formula: The compound according to claim 1, which is represented by: 11 Formula: The compound according to claim 1, which is represented by: 12th equation: The compound according to claim 1, which is represented by: 13th formula: The compound according to claim 1, which is represented by: 14th formula: The compound according to claim 1, which is represented by: 15th formula: The compound according to claim 1, which is represented by: 16th formula: The aniline expressed by the following formula: (In the above formula and inside, R ₁ , R ₂ , R ₃ , R ₄ and
R ₅ represents the meaning defined below): (In the formula, each of R ₁ and R ₂ represents a halogen atom, but R ₁ and R ₂ do not represent a chlorine atom at the same time, R ₃ represents −CF ₂ −CHF−CF ₃ , and R ₄ represents a hydrogen atom, a halogen atom, a methyl group, a methoxy group, or a methylthio group, and R ₅ represents a halogen atom, a methyl group, a methoxy group, or a methylthio group. 17 Formula: The isocyanate represented by the following formula: (In the above formula and inside, R ₁ , R ₂ , R ₃ , R ₄ and
(R ₅ represents the meaning defined below) with a benzamide of the following formula: (In the formula, each of R ₁ and R ₂ represents a halogen atom, but R ₁ and R ₂ do not represent a chlorine atom at the same time, R ₃ represents −CF ₂ −CHF−CF ₃ , and R ₄ represents a hydrogen atom, a halogen atom, a methyl group, a methoxy group, or a methylthio group, and R ₅ represents a halogen atom, a methyl group, a methoxy group, or a methylthio group. 18 In the above formula, each of R ₁ and R ₂ represents a fluorine atom, a chlorine atom or a bromine atom, provided that
R ₁ and R ₂ do not represent chlorine atoms at the same time, and R ₃ is −
Claim 16 or 17 of a compound representing _CF2 -CHF- _CF3 , _R4 representing a hydrogen atom, a fluorine atom, or a chlorine atom, and _R5 representing a fluorine atom, a chlorine atom, or a methoxy group manufacturing method. 19 At least one of the following formulas as an active ingredient: (In the formula, each of R ₁ and R ₂ represents a halogen atom, but R ₁ and R ₂ do not represent a chlorine atom at the same time, R ₃ represents −CF ₂ −CHF−CF ₃ , and R ₄ represents hydrogen atom, halogen atom, methyl group, methoxy group or methylthio group, and R ₅ represents a halogen atom, methyl group, methoxy group or methylthio group) together with a suitable carrier and/or auxiliary agent. Contains insecticides and acaricides. 20 In the above formula, each of R ₁ and R ₂ represents a fluorine atom, a chlorine atom or a bromine atom, provided that
R ₁ and R ₂ do not represent chlorine atoms at the same time, and R ₃ is −
A patent claim containing as an active ingredient at least one compound representing CF2 _- CHF- _CF3 , _R4 representing a hydrogen atom, a fluorine atom, or a chlorine atom, and _R5 representing a fluorine atom, a chlorine atom, or a methoxy group. The insecticide and acaricide according to item 19. 21 In the above formula, R ₁ represents a fluorine atom, and R ₂ represents a fluorine atom, a chlorine atom, or a bromine atom, or R ₁ represents a chlorine atom, R ₂ represents a fluorine atom, and R ₃ represents a fluorine atom. −CF ₂ −CHF−CF ₃ and R ₄
represents a hydrogen atom, a fluorine atom or a chlorine atom,
The insecticide and acaricide according to claim 20, which contains as an active ingredient at least one compound in which R ₅ represents a fluorine atom, a chlorine atom, or a methoxy group. 22 In the above formula, R ₁ represents a fluorine atom, R ₂ represents a fluorine atom, a chlorine atom, or a bromine atom, R ₃ represents -CF ₂ -CHF-CF ₃ , and R ₄ represents a hydrogen atom or a fluorine atom. 22. The insecticide and acaricide according to claim 21, which contains as an active ingredient at least one compound in which R ₅ represents a fluorine atom, a chlorine atom, or a methoxy group.