JPH0251546B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention provides novel substituted N-benzoyl-N′-2,
The present invention relates to 5-dichloro-4-hexafluoropropyloxyphenylurea, a method for producing the same, and a composition containing the compound. (Means for solving the problem) The present invention is based on the following formula: (In the formula, R ₁ represents a hydrogen atom, a fluorine atom, a chlorine atom, or a methoxy group, and R ₂ represents a fluorine atom, a chlorine atom, or a methoxy group.) and salts thereof. . In particularly preferred compounds of the formula, R ₁ is a hydrogen atom;
represents a fluorine atom or a chlorine atom, and R ₂
represents a fluorine atom, a chlorine atom or a methoxy group. A more preferred compound of the formula is one in which R ₁ and R ₂ simultaneously represent a fluorine atom, a chlorine atom or a methoxy group. Moreover, further particularly preferred compounds of the formula are:
Compounds in which R ₁ represents a hydrogen atom, a fluorine atom, or a chlorine atom, and R ₂ represents a fluorine atom or a chlorine atom, and R ₁ represents a hydrogen atom, a fluorine atom, and R ₂ represents a fluorine atom or A compound that represents a chlorine atom. The compound represented by the formula
2061780 and 3240975)). Therefore, for example, a compound represented by the formula: (a) A compound represented by and the following formula: (In the formula, R ₁ and R ₂ represent the above meanings.) or (b) the following formula: A compound represented by and the following formula: (In the formula, R ₁ and R ₂ represent the above meanings.) or (c) a compound represented by the above formula, and the following formula: (In the formula, R ₁ and R ₂ have the above meanings, and R represents an alkyl group having 1 to 8 carbon atoms, which is unsubstituted or substituted by a halogen atom, preferably a chlorine atom.) It can be obtained by reacting the compound with a compound obtained by converting the obtained compound into a salt, if desired. The above manufacturing methods (a), (b), and (c) can be carried out preferably under normal pressure and in the presence of an organic solvent or a 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 halogen 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. Method (a) usually involves a temperature range of -10° to +200°C, preferably 0° to 100°;
For example, it is carried out at room temperature and optionally in the presence of an organic base such as triethylamine. Method (a)
also constitute an object of the invention. Process (b) is carried out in the temperature range from 0° to 150° C., preferably at the boiling point of the solvent used, and optionally in the presence of an organic base such as pyridine and/or an alkali metal or alkaline earth metal, preferably sodium Do this by adding For process (c), ie, the reaction of the urethane of the formula with the aniline of the formula, a temperature range of about 60° to the boiling point of the reaction mixture is preferred and the solvent used is preferably an aromatic hydrocarbon, e.g. These include toluene, xylene, and chlorobenzene. The formulas and starting materials of the formulas are known and can be prepared by methods analogous to those known. The starting aniline of the formula is a new compound. The compound represented by the formula can be found in the Journal of Organ Chemistry (J.Org.Chem.) 29
(1964), 1, by a method similar to that described in 1: It can be prepared by hydrogenation of a suitable substituted nitrobenzene of the formula (see also the documents cited therein) by methods known per se. However, anilines of the formula can also be obtained by chemical reduction (e.g. S _o () chloride/HCl) of nitro compounds of the formula (Houben-Weyl, “Methoden "Methoden d.Org.Chemie"
11/1, 422]. The nitro compound of the formula itself can be prepared by haloalkylating 2,5-dichloro-4-nitrophenol. Another method for preparing anilines of the formula is to haloalkylate acylated 2,5-dichloro-4-hydroxyanilines in a corresponding manner and then remove the acyl group, for example by acid hydrolysis, or Or 2,5-dichloro-
By carrying out haloalkylation with a salt of 4-hydroxyaniline, such as chlorine hydrate. Benzoyl isocyanate of the formula can be obtained in particular as follows [J.Agr.Food Chem. 21 ,
See pages 348 and 993; 1973]: 4-(hexafluoropropyloxy)phenyl isocyanate (boiling point 95° C./0.01 torr), which is novel in itself, can be prepared by phosgenating, for example, aniline of the formula by methods commonly used in the art. It can be manufactured by The benzamides of the formula used as further starting materials are known (see, for example, Beilstein, "Handbuch der organischen Chemie", vol. 9).
(See page 336). Urethanes of the formula can be prepared by reacting benzoyl isocyanates of the formula with suitable alcohols or reacting benzamides of the formula with the corresponding esters of chloroformic acid Cl-COOR in the presence of a base by methods known per se. It can be obtained by reacting with According to the invention, the novel compounds of the formula and their salts not only exhibit excellent insecticidal activity, but are also easily soluble in solvents and diluents, especially organic solvents, and are even easier to formulate. Of particular mention are the metal salts, especially the alkali metal and alkaline earth metal salts, preferably the sodium and potassium salts, of the compounds of the formula according to the invention. These salts are prepared in a manner known per se by reacting the compounds of the formula with metal alkanolates, such as sodium ethylate or potassium methylate. The salt obtained can be converted into the desired salt of another metal, for example by interaction with another alkanolate. Of particular importance are the salts of the compounds of the formula with organic bases, the essential feature of which is the presence of a quaternary nitrogen atom. Such a salt has the following formula a: (wherein R ₁ and R ₂ represent the above meanings, and
represents a cation of an organic base. ).
X is preferably one of the following organic cations _: ( _CH3 ) _{4N ,} ( _C2H5 ) _4N , (n- _C3H7 ) _4N ,
(i-C ₃ H ₇ ) ₄ N, (n-C ₄ H ₉ ) ₄ N,

【formula】

【formula】

[Formula] (C ₄ H ₉ ) ₃ NH,

[Formula] and [CH ₃ − (CH ₂ ) _o −] ₃ N-CH ₃ (in the above formula, n represents an integer from 8 to 12). Salts of formula a also consist of mixtures of these salts with different cations. Salts of the formula a are obtained by reaction of compounds of the formula with the corresponding ammonium hydroxide of the formula: X (OH), where X has the meaning given above. It can be manufactured by a method known per se. Surprisingly, the present inventors have discovered that the compounds of the present invention and their salts have excellent characteristics as pest control agents, and at the same time are well tolerated by plants and are effective against warm-blooded animals. It was discovered that it has low toxicity. They are particularly suitable for controlling insects and representatives of the order Acarina that attack plants and animals. In particular, the compound represented by the formula may be of the order Lepidoptera, Coleoptera, Homoptera, Heteroptera,
Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Chilling beetles Control of insects such as the orders Psocoptera and Hymenoptera, and the families Ixodidae, Argasidae, Tetranychidae and Dermanyssidae of the order Acarina. suitable for Compounds of formula
In addition to their action against insects (e.g. Spodoptera domestica) and mosquito larvae, plant-damaging insects, especially plant-feeding insects, in ornamental and useful crops, especially in cotton [e.g.
littoralis) and Heliothis virescens] and in fruit and vegetable crops (e.g. Laspeyresia pomonella, Leptinotarsa decemlineata)
It is also suitable for controlling P. decemlineata and Epilachna varivestis. The compounds of the formula exhibit a marked ovicidal and especially larvicidal action against insects, especially against the larvae of insects that cause feeding damage. When the compound of the formula is taken with the diet during the adult stage, a reduction in hatching rate and egg production is observed in a number of insect species, particularly in the Coleoptera, Anthonomus grandis. Compounds of the formula may also be used to control Lucilia sericata in farm animals and production livestock.
It can also be used to control ectoparasites such as, preferably by treating animals, barns, barns, stables, etc., as well as pastures. The compounds of the formula are also suitable for controlling the following types of mites which are harmful to fruit trees and vegetables: Tetranychus urticae, Tetranychus cinnadarinus, Panonychus ulmi, false clover spider mite.
Bryobia rubrioculus), Panonychus citri, Eriophyespiri, Eriophyesribis, Eriophyes vitis, Tarsonemus pallidus, Phyllocoptes vitis, Phyllocoptes
Oleivora (Phyllocoptes oleivora). A good pest control action of the compounds of the formula according to the invention corresponds to a mortality of at least 50-60% of the above 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 organophosphorus compounds, nitrophenols and their derivatives, formamide, urea, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis.
Examples include formulations. The compounds of the formula are used in neat form or as compositions, preferably with the auxiliaries customary in formulation technology, and can be prepared as emulsion concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, etc. by known methods. They are formulated in aqueous solutions, powders, granules, and encapsulates, eg, with polymeric substances. The method of application, such as spraying, sprinkling or pouring, as well as the nature of the composition, will be chosen depending on the intended audience and environment of use. Preparations, i.e. compositions containing a compound of the formula (active ingredient) and, where appropriate, solid or liquid auxiliaries, can be prepared, for example, by combining the active ingredient with a solvent, a solid carrier and, where appropriate, a surface-active compound. (surfactants) by homogeneous mixing and/or milling with fillers such as 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; fats 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 cyclohexane; N-methyl-2-pyrrolidone,
Strong polar solvents such as dimethyl sulfoxide or dimethyl sulformamide; and epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water. Solid carriers which can be used, for example in dusts 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, especially dolomite or pulverized plant debris. Depending on the nature of the compound of the formula to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants with good emulsifying, dispersing and wetting properties. The term "surfactant" is to be understood to include mixtures of surfactants. Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds. Suitable soaps are alkali metal salts, alkaline earth metal salts, or unsubstituted or substituted ammonium salts of higher fatty acids (C ₁₀ -C ₂₂ ), such as oleic acid or stearic acid, or natural soaps obtained, for example, from coconut oil or tallow. Sodium or potassium salts of fatty acid mixtures. Fatty acid methyltaurate salts may also be used. 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 an alkyl group having from 8 to 22 carbon atoms, which also includes the alkyl part of an 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. Corresponding phosphates, such as salts of the phosphoric esters of p-nonylphenol adducts containing 4 to 14 mol of ethylene oxide, are also suitable. The nonionic surfactants are preferably aliphatic or acyclic alcohols or polyglycol ether derivatives of saturated or unsaturated fatty acids and alkylphenols, which derivatives have a concentration of 3 to 30
Glycol ether groups (aliphatic) contain 8 to 20 carbon atoms in the hydrocarbon portion and alkylphenols 6 to 18 carbon atoms in the alkyl portion. Other suitable nonionic surfactants are polyethylene oxide and polypropylene glycol,
A water-soluble adduct of ethylene diamine polypropylene glycol and an alkyl polypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, the adduct containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol. Contains ether. These compounds usually contain 1 per propylene glycol unit.
Contains from 5 to 5 ethylene glycol units. Typical examples of nonionic surfactants are nonylphenol-polyethoxyethanol, castor oil polyglycol ether, polypropylene/polyethylene oxide adduct, tributylphenoxypolyethoxyethanol, polyethylene glycol, and octylphenoxyethoxyethanol. be. 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 a lower unsubstituted or halogenated 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, for example stearyltrimethylammonium chloride or benzyl di-(2-chloroethyl)ethylammonium bromide. Surfactants customary in the pharmaceutical industry are described, for example, in the following publication:
Annual (Mc Cutcheon's Detergents and
Emulsifiers Annual)”, Matsuku Publishers, Ringwood, New Jersey, 1979; Dr. Helmut
Stache, “Tensid-Tashenbuch”, Carl Hanser Verlag, Millichen and Vienna. Pest control compositions usually contain from 0.1 to 99%, preferably from 0.1 to 95%, of a compound of formula or a combination thereof with other insecticides or acaricides.
%, solid or liquid adjuvants from 1 to 99.9%, and surfactants from 0 to 25%, preferably from 0.1 to 25%. Although commercial products are preferably formulated as concentrates, consumers typically use dilute formulations with substantially lower concentrations. The compositions may also contain other additives such as stabilizers, antifoams, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients for special effects. Example 1 (a) 2,5-dichloro-4-(1,1,2,3,
Preparation of 3,3-hexafluoropropyloxy)aniline 47 g of 4-acetylamino-2,5-dichlorophenol are stirred with 154 g of 90% potassium hydroxide solution and 130 ml of dimethylformamide in an autoclave. Next, 75.8 g of hexafluoropropylene is press-fitted into the closed autoclave. The mixture is stirred in an autoclave under pressure at 70° C. for 20 hours. After cooling, the mixture is concentrated on a rotary evaporator and the residue is redissolved in methylene chloride. Wash the resulting solution with water,
Dry with Na ₂ SO ₄ and concentrate. The crude product obtained as a residue was chromatographed by passing it through a silica gel column (length: 1 m; diameter: 10 cm) and eluting with a mixture of toluene:acetone = 11:1. 4-acetylamino-2,5-dichloro-1 in the form
-(1,1,2,3,3,3-hexafluoropropyloxy)benzene (melting point: 93-95℃)
26g of this compound was added to ethanol under reflux.
Keep together with 110 ml and 35.6 ml of 37% hydrochloric acid for 10 hours.
The reaction mixture is then concentrated, diluted with ice/water and made slightly alkaline. The product is extracted from the mixture with methylene chloride. The organic extract layer was washed with water, dried with Na ₂ SO ₄ and
and concentrate. The residue is concentrated by distillation: The title compound represented by has a boiling point of 81-83℃/
Obtained as a colorless liquid at 0.05 torr. (b) N-(2,6-trifluorobenzoyl)-
N′-[2,5-dichloro-4-(1,1,2,
3,3,3-hexafluoropropyloxy)
Production of phenyl]urea 2,5-dichloro-4-(1,1,2,3,
4.7 g of 3,3-hexafluoropropyloxy)aniline were dissolved in 50 ml of dry toluene with stirring and, with removal of moisture, 2.
6-difluorobenzoyl isocyanate 2.62
A solution of g dissolved in 10 ml of dry toluene is added at room temperature. The batch is stirred for an additional 10 hours at room temperature. Approximately 75% of the solvent was then removed by rotary evaporation, and the precipitated residue was filtered off with suction, washed with a small amount of cold toluene and hexane, and dried under vacuum, with a melting point of 174-175.
In the form of a crystalline white powder at °C the following formula: The title compound represented by (Compound 1) is obtained. The following compounds of the formula were prepared in a manner analogous to the above method:

【table】

【table】

[Table] (c) Production of sodium salt represented by the formula N-(2,6-difluorobenzoyl)-
N′-[2,5-dichloro-4-(1,1,2,
3,3,3-hexafluoropropyloxy)
Phenyl] urea 9.58g, anhydrous methanol 20ml
Suspend in A solution of 0.43 g of sodium dissolved in 30 ml of absolute methanol is added in portions to this suspension while stirring. The clear solution formed is then concentrated. The residual product, when dried under reduced pressure at room temperature, has a melting point of 169-171°C (decomposition).
The following equation with: The title compound is obtained in the form of colorless crystals (compound 10). A salt of compound 2 represented by the following formula can also be prepared by the same operation as above:

[Table] (d) Production of tetrabutylammonium salt of compound 1 N-(2,6-difluorobenzoyl)-
N′-[2,5-dichloro-4-(1,1,2,
3,3,3-hexafluoropropyloxy)
2.56 g of phenyl]urea are suspended in 30 ml of methanol. While stirring, 5.2 g of a methanolic solution containing 1.3 g of tetra-n-butylammonium hydroxide are added to this suspension, forming a clear solution. The solution is concentrated and the remaining crude product is suspended in hexane.
The suspension is filtered with suction and the excess residue is washed with hexane and then dried, melting point 110°C.
In the form of colorless crystals with the following formula: The title compound represented by is obtained (compound
12). Salts of formula a below can also be prepared according to this procedure: Example 2 Formulation of the active ingredient of the formula according to Example 1 or a combination thereof with other insecticides or acaricides (% is % by weight throughout)

[Table] Wettable powders that can be diluted with water to obtain a suspension of the desired concentration by thoroughly mixing the active ingredient or compound with the auxiliaries and then thoroughly grinding the mixture in a suitable mill. is obtained. 2 Emulsified neat compounds or formulations 10% Octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (36 moles of ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50 % By diluting this emulsion stock solution with water, an emulsion of a desired concentration can be obtained.

By mixing the active ingredient with the carrier and milling the mixture in a suitable mill, a ready-to-use powder is obtained. 4 Compounds or formulations in extruded granule format 10% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 87% Active ingredients or formulations mixed with auxiliaries.
Grind and then moisten the mixture with water. The mixture is extruded and dried in a stream of air. 5 Compound or formulation in coated granules 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. 6 Compounds or mixtures in suspension form 40% Ethylene glycol 10% Nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% Sodium lignosulfonate 10% Carboxymethyl cellulose 1% 37% formaldehyde aqueous solution 0.2% 75% aqueous emulsion silicone oil
0.8% Water 32% A suspendable concentrate is obtained by homogeneously mixing the finely ground active ingredient or formulation with auxiliaries and diluting with water to obtain a suspension of the desired concentration. Example 3 Action against the house fly (Musca domestica) Fill each beaker with 50 g of freshly prepared nutrient medium for maggots. An aliquot of a 1% acetone solution of each test compound is pipetted into the nutrient medium in a beaker to give an active ingredient concentration of 800 ppm. Then, after thoroughly mixing the medium, the acetone is allowed to evaporate for at least 20 hours. Twenty-five one-day-old housefly maggots are placed in a beaker containing the test nutrient medium containing each active ingredient at the indicated concentrations. After the maggots have pupated, separate the pupae from the medium by flushing them 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. The measurement is 10
This is done by counting the number of flies that emerge from pupae after a day. In this test, the compound of the formula obtained in Example 1 showed a good effect. Example 4 Effect on Lucilia sericata 1 ml of an aqueous formulation containing 0.5% of the test compound was
Add to 9 ml of nutrient medium at 50°C. Then about 30
The insecticidal effect is determined by adding newly hatched Lucilia sericata larvae to the nutrient medium and assessing mortality after 48 and 96 hours. In this test, the compound of formula obtained in Example 1 showed good action against Lucilia sericata. Example 5 Effect on the Egyptian Aedes ae¨gypti The test compound was applied to the surface of 150 ml of water in a beaker.
Pipette a certain amount of 0.1% acetone solution to obtain a solution with a concentration of 800 ppm. After the acetone evaporates, 30 to 2 day old Egyptian Aedes mosquito larvae
Forty animals are placed in a beaker containing the test compound. Count the number of dead insects after 1, 2 and 5 days. In this test, the compound of the formula according to Example 1 showed good activity against the Egyptian Aedes mosquito. Example 6 Insecticidal action against feeding insects Cotton plants with a height of about 25 cm placed in flowerpots are sprayed with aqueous emulsions containing test compounds at concentrations of 0.75, 12.5 and 100 ppm, respectively. After the spray coating has dried, Spodoptera littoralis
L ₃ stage larvae of L. littoralis and Heliothis virescens are inhabited on cotton plants. The test is conducted at 24°C and 60% humidity. Check the mortality rate (%) of the test insects after 120 hours. Compound 1 according to Example 1 shows a mortality rate of 80 to 100% against Spodoptera larvae and Heliothis larvae at 0.75 ppm. Compound 3 shows 80 to 100% mortality against Spodoptera larvae at 12.5 ppm and at 100 ppm against Heliothis larvae. Example 7 Mexican broad bean weevil (Epilachna)
Effect on Phaseolus vulgaris plants (dwarf) 15 to 20 cm high
(beans) are sprayed with an aqueous emulsion of the test compound at a concentration of 800 ppm. After the sprayed coating has dried, the Mexican bean beetle
Populate each plant with 5 larvae of L ₄ stage. Immediately cover the treated plants with a plastic cylinder and top with copper wire mesh. This test was conducted at 28℃.
Performed at 60% relative humidity. Check the mortality rate after 2 and 3 days. The insects in this test are observed for an additional 3 days to evaluate inhibition of feeding (anti-feeding effect) and inhibition of growth and molting. In this test the compound of the formula according to Example 1 showed a good effect. Example 8 Ovicidal action against Heliotis viretscens A hydratable equivalent containing 25% by weight of the test compound is mixed with sufficient water to produce an aqueous emulsion containing the active ingredient at a concentration of 800 ppm. One day old Heliothis viretscens eggs placed on cellophane are immersed in the emulsion for 3 minutes and collected by suction onto a round filter. Place the treated eggs in a Petri dish and keep it dark. After 6 to 8 days, check the hatching rate compared to the untreated control group. In this test, the compound of the formula according to Example 1 showed good ovicidal action. Example 9 Laspeyresia pomonella
(Pomonella pomonella) eggs La Peiresia Pomonella eggs within 24 hours after spawning are 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 keep at a temperature of 28 °C. 6
After days, evaluate hatching and mortality of larvae from treated eggs. In this test the compound of the formula according to Example 1 showed a good effect. Example 10 Anthonomous grandis
Effects on reproduction of Anthonomus grandis) Adults of Anthonomus grandis within 24 hours of emergence are placed in groups of 25 in closed cages. The cage is immersed for 5 to 10 seconds in an acetone solution containing 400 ppm of test compound. Once the beetles are dry, place them in a covered dish containing food;
Leave them alone for mating and spawning. Eggs are flushed under running water two to three times a week, counted, sterilized by placing them in an aqueous disinfectant for 2 to 3 hours, and then placed in a dish containing suitable larval food. After 7 days, the number, ie the number of hatched larvae, is checked to determine the mortality of the eggs. The persistence of the reproductive inhibitory effect of the test compound is determined by examining eggs over a period of 4 weeks.
The evaluation is made by the reduction in the number of eggs and hatched larvae compared to the untreated control group. In this test, compounds 1 and 3 according to Example 1 were
Shows 100% ovicidal activity. Example 11 Effect on Anthonomus grandis (adult) Two cotton plants at the six-leaf stage in pots are sprayed with a hydratable emulsion containing the test compound at a concentration of 400 ppm. After the sprayed coating has dried (approximately 1
1/2 hour), each plant was populated with 10 adult beetles (Anthonomus grandis). 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. Treated plants at 25°C and 60% relative humidity
Keep it. 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 the above test, the compound represented by the formula of Example 1 showed good activity. Example 12 Comparative test of insecticidal activity (1) Test compounds The following compounds were used to examine their insecticidal activity.

【table】

[Table] The test compounds used for this comparative test were manufactured according to the method described in JP-A-58-26858, US Pat. No. 4,518,804, and the present specification, and each compound was have the melting points stated therein. (2) Test method Compounds were tested simultaneously under the same conditions and order for the following test procedures A, B, and C. Test A - Effect on Spodoptera Iittoralis Potted cotton plants approximately 25 cm in height were treated with an aqueous suspension of the test compound (an emulsifying wettable powder formulation containing 25% by weight of the respective active substance). ) was atomized using a compressed air atomizer. The sprayed suspensions contained 0.8 and 0.8 of the test compound, respectively.
Contains 0.4ppm. Potted cotton plants were sprayed with an aqueous suspension of the test compound until the drop point was reached. After drying of the spray coating, Spodoptera littoralis larvae of the first larval stage were placed on top of the treated cotton plants. Each plant was populated with 10 larvae. Two plants were used for each test, ie for each concentration of test compound. After 6 days of infection of the plants, the percentage mortality of the larvae was evaluated. Test at a temperature of 24℃, 60
% relative humidity. Test B - Effect on Heliothis virescens Heliothis virescens larvae at the first larval stage are used as test insects and potted soybean plants are used as host plants, with test compound concentrations of 3.0 and 1.5 ppm. Test A above was repeated with this change. Test C - Plutella xylostella
xylostella) Chinese cabbage (Brassica pekinensis) in the fourth leaf stage
potted plants were sprayed with an aqueous suspension of the test compound (obtained from an emulsifying wettable powder formulation containing 25% by weight of the respective active substance) using a compressed air atomizer. The sprayed suspensions contain 0.8 and 0.2 ppm of test compound, respectively. Potted plants were sprayed with an aqueous suspension of the test compound until the drop point was reached. After the spray coating has dried,
Plutella xylostella larvae at the second or third larval stage were allowed to live on treated Chinese cabbage plants. for each plant
Inhabited by 10 larvae. Each plant was populated with 10 larvae. Two plants were used for each test, ie for each concentration of test compound. Five days after infection of the plants, the percentage mortality of the larvae was evaluated. The test was carried out at a temperature of 24°C and 60% relative humidity. (3) Test results The insecticidal activity of the compounds measured according to Tests A, B and C above is given in the following table.

[Table] The results obtained show that the compounds and are superior in comparison to the compounds with respect to insecticidal activity, in particular the compounds are inactive or almost inactive against the test insects at low concentrations, while the compounds and are 0.8 Even in ppm
It has been shown to be highly active against Plutella xylostella.

Claims (1)

[Claims] Primary formula: (In the formula, R ₁ represents a hydrogen atom, a fluorine atom, a chlorine atom, or a methoxy group, and R ₂ represents a fluorine atom, a chlorine atom, or a methoxy group.) or a salt thereof. 2. The compound according to claim 1, wherein in the formula, R ₁ represents a hydrogen atom, a fluorine atom or a chlorine atom, and R ₂ represents a fluorine atom, a chlorine atom or a methoxy group. 3. The compound according to claim 1, wherein in the formula, R ₁ and R ₂ simultaneously represent a fluorine atom, a chlorine atom, or a methoxy group. 4. The compound according to claim 1 or 2, wherein in the formula, R ₁ represents a hydrogen atom, a fluorine atom, or a chlorine atom, and R ₂ represents a fluorine atom or a chlorine atom. 5. The compound according to claim 4, wherein in the formula, R ₁ represents a hydrogen atom or a fluorine atom, and R ₂ represents a fluorine atom or a chlorine atom. Sixth formula: The compound according to claim 3, which is represented by: 7 Formula: The compound according to claim 5, which is represented by: 8th formula: The compound according to claim 3, which is represented by: 9 Formula: The compound according to claim 5, which is represented by: 10th formula: The compound according to claim 2, which is represented by: 11 Formula: The compound according to claim 5, which is represented by: 12th equation: The compound according to claim 2, which is represented by: 13th formula: The compound according to claim 3, which is represented by: 14th formula: The compound according to claim 2, which is represented by: 15. The salt of the compound according to claim 1, which is a metal salt of the compound represented by the above formula. 16. A salt of the compound according to claim 1, which is a salt of the compound represented by the above formula and an organic base. 17 In the above formula, claim 1 in which a quaternary nitrogen atom is present
A salt of the compound described in item 6. 18 Formula: A compound represented by and the following formula: (wherein R ₁ and R ₂ represent the following meanings) and, if desired, converting the obtained compound into a salt: (In the formula, R ₁ represents a hydrogen atom, a fluorine atom, a chlorine atom, or a methoxy group, and R ₂ represents a fluorine atom, a chlorine atom, or a methoxy group.) A method for producing a compound or a salt thereof. 19 As an active ingredient, the following formula: (In the formula, R ₁ represents a hydrogen atom, a fluorine atom, a chlorine atom, or a methoxy group, and R ₂ represents a fluorine atom, a chlorine atom, or a methoxy group.) or a salt thereof,
Pest control compositions containing suitable carriers and/or other additives.