JPH0349901B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel halogen-substituted N-(3-trifluoromethyl-4-halogenoalkoxy-phenyl)-N'-benzoyl urea, a process for its preparation, and an insecticide containing the compound. The halogen-substituted N-(3-trifluoromethyl-4-halogenoalkoxy-phenyl)-N-benzoyl urea according to the invention has the following formula: (In the formula, R ₂ and R ₃ represent a fluorine atom,
Alternatively, R ₂ and R ₃ represent a chlorine atom, or R ₂ represents a fluorine atom or a chlorine atom and R ₃ represents a hydrogen atom. ). Among the compounds represented by the formula according to the present invention,
Preferred compounds in terms of their action as pest control agents are compounds in which R ₂ and R ₃ each represent a fluorine atom or R ₂ and R ₃ each represent a chlorine atom, and R ₂ represents a fluorine atom or a chlorine atom. , R ₃ represents a hydrogen atom. The compounds of the formula can be prepared by the following method (see DE 2123236 and DE 2601780). Thus, for example, a compound of the formula: a) The compound represented by the following formula: or b) with the following formula: A compound represented by the following formula, optionally in the presence of an organic or inorganic base: It can be produced by reacting with a compound represented by: In these formulas, , and, R ₂ and ₃ represent the meanings given in the formulas. Processes a) and b) above are preferably carried out under normal pressure and in the presence of an inert organic solvent or diluent. Suitable solvents or diluents include, for example: ethers and ether compounds such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylated carboxylic acid amides; aliphatic, aromatic and halogenated Hydrocarbons, especially benzene, toluene, xylene,
Chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; nitrites such as acetonitrile or propionitrile; dimethyl sulfoxide and ketones such as methyl ethyl ketone,
Examples include methyl isopropyl ketone and methyl isobutyl ketone. Method a) is usually -
It is carried out at a temperature of 10 to 100°C, preferably 0 to 25°C, optionally in the presence of an organic base, such as triethylamine. Method b) is 0
C. to 150.degree. C., preferably at the boiling point of the solvent used, optionally in the presence of an organic base such as pyridine, with addition of an alkali metal or alkaline earth metal, preferably sodium. The starting materials of the formulas and are known or can be prepared by methods analogous to known methods. Therefore, substituted anilines of the formula can be prepared by methods known from the literature:
For example, hydrogen 2-trifluoromethyl-4-nitrophenol is reduced in the presence of acetic anhydride [Journal of Organic Chemistry (J.
Org. Chem.), Vol. 27, p. 4660, 1962], and the resulting 2-trifluoromethyl-4-acetamino-phenol was reported in Am. So., Vol. 73, p. 5831, 1951. They may be prepared by etherification with appropriate halogen-substituted alkenes in a manner analogous to that described. Subsequently, the N-acetyl group is removed by a conventional method to obtain the aniline represented by the formula. Some of these anilines are J.
Org.Chem., Vol. 29, p. 1, 1964 (see further references cited therein). One particular method for obtaining benzoyl isocyanate represented by the formula is the following reaction formula: [See Journal of Agricultural and Food Chem., Vol. 21, pp. 348 and 993, 1973]. Substituted phenyl isocyanates of the formula may be prepared, for example, by reacting a suitable aniline of the formula with phosgene using normal, conventional means. The benzamides of the formula used as starting materials can be prepared in a number of known ways [Beilstein
Author: Handbuch der Organizien
“Handbuch der organischen”
9, p. 336]. It is already known that certain N-phenyl-N'-benzoyl-ureas have insecticidal properties (DE 2123236, DE 2504982 and DE 2504982). Publication No. 2537413, Belgian Patent No. 832304,
843906 and 844066, and U.S. Pat. Nos. 4,085,226 and 4,089,975). Furthermore, German Patent Publication No. 2601780, no.
No. 2726684 and No. 2820696 also describe halogen-substituted N-halogenoalkoxy-N'-benzoyl ureas which are insecticidal. The inventors have surprisingly found that N-(3-trifluoromethyl-
4-halogenoalkoxy-phenyl)-N'benzoyl urea has a high tolerance to plants and negligible toxicity to warm-blooded animals, while being effective against pests infecting plants and animals, especially insect larvae. have been found to exhibit greater potency than said compounds known from the prior art. The compounds represented by the formula are particularly suitable for the orders Lepidoptera, Coleoptera, Homoptera, Heteroptera,
Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Suitable for controlling insects such as Psocoptera and Hymenoptera. The compound represented by the formula damages plants through feeding damage. Insects that attach to cotton, such as ornamental and beneficial plants, such as Spodoptera Littoralis and Heiothis virescens, and insects that attach to vegetables, such as Colorado potato beetles, Leptinotarsa decemineata.
Suitable for controlling pests. The compounds of the formula are characterized by a remarkable activity against insects in their larval stage, especially those that damage plants by feeding. When the compound of the formula is ingested with food during the adult stage, it is often found that insects of the order Coleoptera, e.g.
Reduced egg production and/or reduced hatching may be observed in Anthonomus grandis. Furthermore, the compound represented by the formula may be, for example, an animal,
It is suitable for controlling ectoparasites of livestock and productive animals, such as the gold fly (Lucilia sericata), by treating livestock sheds and pastures. The action of the compounds of the invention or of the medicaments containing them can be significantly extended and adapted to the given environment by the addition of other insecticides and/or acaricides. Suitable additives include, for example, active substances such as organophosphorus compounds, nitrophenols and their conductors, formamidine, urea, carbamates, pyrethroids and chlorinated hydrocarbons. The compounds of the formula can also be combined with particular advantage with substances that enhance their pesticidal action. Examples of such compounds include piperonyl butoxide, propionyl ether, propionyl oxime, propynyl carbamate and propynyl phosphonate, 2-(3,
4-methylenedioxyphenoxy)-3,6,9
-trioxaundecane or S,S,S-tributylphosphorotrithioate. The compounds of the formula can be used on their own or together with suitable carriers and/or additives. Suitable carriers and additives may be solid or liquid and include substances commonly used in conventional formulations, such as natural or recycled substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders. and/or fertilizer, etc. In application, the compounds represented by the formula are usually powders, emulsion concentrates, granules, dispersants,
They can be prepared in the form of sprays, solutions or suspensions, and their preparation can be carried out in a manner well known in the art. Mention may also be made of the home dipping method and the spray lace method, in which aqueous preparations are used. These preparations are particularly suitable for controlling animal parasites. To prepare the medicament according to the invention, the active ingredient of the formula is homogeneously mixed with a suitable carrier in a manner known per se, optionally with the addition of dispersants or solvents inert to the active ingredient. and/or grind. The active ingredient can be processed into the following dosage forms and used. Solid preparations: powders, dusting powders or granules (coated granules, impregnated granules and homogeneous granules); liquid preparations: (a) water-dispersible active ingredient concentrates: wettable powders, pastes and emulsions; (b) solutions in said preparations. The content of active ingredients is 0.1-95%. The active ingredient represented by the formula is formulated, for example, as follows. Powders: The following ingredients are used to prepare (a) 5% and (b) 2% powders. (a) Active ingredient 5 parts talc 95 parts (b) Active ingredient 2 parts highly dispersed silicic acid 1 part talc 97 parts The active ingredient is mixed with the carrier and milled. Granules: The following ingredients are used to prepare the 5% granules: Active ingredients 5 parts Epoxidized vegetable oil 0.25 parts Cetyl polyglycol ether 0.25 parts Polyethylene glycol 3.50 parts Kaolin (particle size 0.3-0.8 mm) 91 parts Epoxidized active ingredient The mixture is dissolved in 6 parts of acetone and then the polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin and the acetone is subsequently evaporated under reduced pressure. Wettable powders: (a) 40%, (b) and (c) 25% and (d) 10% wettable powders are prepared using the following ingredients: (a) Active ingredient 40 parts Sodium ligninsulfonate 5 parts Sodium dibutyl-naphthalene sulfonate 1 part Silicic acid 54 parts (b) Active ingredients 25 parts Calcium lignin sulfonate 4.5 parts Chiyok/Hydroxyethylcellulose mixture from Xiangpen (1:1) 1.9 parts Sodium dibutylnaphthalene sulfonate
1.5 parts silicic acid 19.5 parts Chiyok from Xiangpen 19.5 parts kaolin 28.1 parts (c) Active ingredients 25 parts isooctylphenoxy-polyoxyethylene-ethanol 2.5 parts Chiyok from Xiangpen/hydroxyethyl cellulose mixture (1:1) 1.7 parts silicic acid Sodium aluminum 8.3 parts Diatomaceous earth 16.5 parts Kaolin 46 parts (d) Active ingredients 10 parts Mixture of sodium salts of saturated fatty alcohol sulfates 3 parts Naphthalene sulfonic acid/formaldehyde condensate 5 parts Kaolin 82 parts The active ingredients are combined in a suitable mixer. Homogeneous mixing with the additives and subsequent milling of the mixture in suitable mills and rollers yield wettable powders which can be diluted with water to give a suspension of the desired concentration. Emulsion Concentrates: The following materials are used to prepare (a) 10%, (b) 25% and (c) 50% emulsion concentrates. (a) Active ingredients 10 parts Epoxidized vegetable oil 3.4 parts Complex emulsion consisting of fatty alcohol polyglycol ether and alkylaralkyl sulfonic acid calcium salt 3.4 parts Dimethylformamide 40 parts Xylene 43.2 parts (b) Active ingredients 25 parts Epoxidized vegetable oil 2.5 parts Alkylaryl sulfonate/fatty alcohol polyglycol ether mixture 10 parts dimethylformamide 5 parts xylene 57.5 parts(c) Active ingredients 50 parts tributylphenol-polyglycol ether 4.2 parts calcium-dodecylbenzene sulfonate
5.8 parts cyclohexanone 20 parts xylene 20 parts These concentrates can be diluted with water to obtain an emulsion of the desired concentration. Propellant: The following ingredients are used to prepare (a) 5% and (b) 95% propellant. (a) Active ingredient 5 parts epoxidized vegetable oil 1 part ligroin (boiling range 160-190°C) 94 parts (b) Active ingredient 95 parts epoxidized vegetable oil 5 parts Example 1 3-trifluoromethyl-4-(1,1 ,2,
5.52 g of 3,3,3-hexafluoropropoxy)-aniline were placed in 25 ml of anhydrous ether, followed by the dropwise addition of 3.7 g of 2,6-difluorobenzoyl isocyanate dissolved in 10 ml of anhydrous ether with stirring at room temperature. The mixture was left stirring for 2 hours. The precipitated solids are then filtered off by suction,
It was then washed with anhydrous ether and dried in air. Recrystallized from toluene, melting point 185-187℃
N-[3-trifluoromethyl-4-
(1,1,2,3,3,3-hexafluoropropoxy)-phenyl]-N'-(2,6-difluorobenzoyl)-urea (Compound No. 1) was obtained. The following compounds of formula 1 are prepared by methods analogous to those described above:

Table: Example 2 Effect on Housefly 50 g of the freshly prepared maggot nutrient medium were weighed into each of a set of beakers. A specified amount of a 1% by weight acetone solution of each active ingredient was pipetted into the nutrient medium of each beaker. After thoroughly mixing the nutrient medium, the acetone was allowed to evaporate for at least 20 hours. Then, in each case 25 one-day-old house fly maggots were placed in each beaker containing the treated nutrient medium for active ingredient and concentration. After pupation was complete, the formed pupae were separated from the nutrient medium by flushing with water and placed in a container covered with a perforated lid. The number of shed pupae per batch was counted (toxic effect of the active ingredient on maggot development), and then after 10 days the number of flies emerging from the pupae was determined. Compounds No. 1, 3, 4 and 5 of Example 1 are:
In the above test, it showed more than 90% activity at 800 ppm. Example 3 Effect on gold flies 1 ml of an aqueous solution containing 0.5% of the active ingredient was heated at 50°C.
and added to 9 ml of medium. Then, about 30 newly hatched golden fly maggots were placed in the medium, and each
and 96 hours later, insecticidal activity was determined by determining mortality. Compounds No. 1, 3, 4 and 5 of Example 1 are:
In this test, it showed a mortality rate of over 80% against golden flies. Example 4 Action against the Egyptian Aedes aegypti A solution of 0.1% of the active ingredient in acetone, sufficient to obtain concentrations of 10.5 and 1 ppm in each case, was pipetted onto the surface of 150 ml of water in a container. Moved. After distilling off the acetone, 30 to 40 2-day-old Egyptian Yap mosquito larvae were placed in each container. 1, 2
And mortality was confirmed 5 days later. Compounds No. 1, 3, 4 and 5 of Example 1 are:
In this test, it showed 100% activity (mortality rate) against the Egyptian Aedes mosquito. Example 5 Insecticidal action against feeding insects Cotton plants were sprayed with an aqueous emulsion of 0.05% active ingredient (obtained from a 10% emulsion concentrate). After drying of the spray coating, Spodoptera littoralis larvae at the 3rd larval stage and Heliotheis viretscens larvae at the 3rd larval stage were respectively infected on the cotton plants. The test was conducted at a temperature of 28° C. and a relative humidity of 60%. Mortality, growth and inhibition of molting of hatched larvae were evaluated in each case at 24 hour intervals. Compounds No. 1, 3, 4 and 5 of Example 1 are:
100% against Spodoptera littoralis and Heliotheis viretscens larvae in the above test
showed insecticidal action. Example 6 Epilachna, varibesteis
Effect on Phaseolus vulgaris plants (shrub legume species) approximately 15-20 cm tall.
An aqueous emulsion formulation containing the active ingredient to be tested at a concentration of 500 ppm was sprayed. After drying the spray layer, 10 larvae of Epiracuna varibesteis (Mexican beetle) in the fourth larval stage were added.
infected on each plant. The treated plants were placed in plastic cylindrical containers with fine copper wire mesh lids. Acute effects (% mortality) were determined in each case after 1 and 2 days. The test insects were observed for an additional 3 days in order to also evaluate the damage caused by feeding on the plants (anti-feeding effect) and inhibition to development and molting. Compounds No. 1, 3, 4 and 5 of Example 1 are:
The above tests showed a mortality rate of at least 90%. Example 7 Effect on Leptinotarsa decemlineata (larvae) Potato plants with a height of 15 cm in a cultivation container were uniformly sprayed with an aqueous emulsion preparation with a concentration of the active ingredient to be tested of 500 ppm using a compressed air sprayer. Spray it on and leave it damp until it drips. After the coating on the plants had dried, ie, after about 1.5 hours, the plants were placed in a plastic cylindrical container and the plants were infected with 10 third stage potato beetle larvae. Next, each cylindrical container was covered with a fine copper wire mesh lid and stored in the dark at 28° C. and 60° C. relative humidity. After 1, 2 and 8 days, evaluations were made in each case for mortality (reverse) and rate of plant damage. Compound No. 3 of Example 1 was 100% in the above test.
showed a mortality rate of Example 8 Antononus grandis (Anthonomus.
Chemical sterilization of Antononus grandis) Adults that hatched within 24 hours were relocated in groups of 25 beetles into cages with lattice walls. The cage containing the beetles was then immersed for 5 to 10 seconds in an acetone solution containing 1.0% by weight of the active ingredient to be tested. After drying the beetles again,
Beetles were placed in a covered dish containing food for mating and oviposition. Newly born eggs were washed with running water and removed two or three times a week. Count the number of eggs and use an aqueous sterilizer (e.g. "Actamer B100").
The cells were sterilized by placing in "Actamer B100" for 2-3 hours and then placed in a dish containing the appropriate larval food. The eggs were examined after 7 days to determine whether the eggs had produced larvae or whether they had developed. In order to confirm the duration of the chemical sterilization effect of the tested active ingredients, beetle spawning was observed for about 4 weeks. The evaluation was based on the reduction in the number of eggs laid and the number of larvae hatched by comparing the reduction with an untreated control sample. Compounds No. 1, 3, 4 and 5 of Example 1 are:
It showed good effects in the above tests. Comparative Test Example The following compounds were used to test their insecticidal efficacy.

[Table] Test method Compounds of the present invention and JP-A-1982-
The compounds disclosed in No. 89646 were tested in parallel under the same conditions and in the same series using the following Test Methods A and B. Test A: Insecticide against Spodoptera littoralis Potted cotton plants approximately 25 cm high were sprayed with an aqueous emulsion of the test compound (obtained from an emulsifiable wettable powder formulation) using a compressed air atomizer. The sprayed emulsion contains the test compound at 3.0,
Contains 0.75 and 0.2 ppm. After drying of the spray film, Spodoptera littoralis larvae of the third larval stage were infected onto the treated cotton plants. Each plant is
Infected with 10 larvae. Larval mortality was also evaluated 6 days after plant infection. The test was carried out at a temperature of 24°C and a relative humidity of 60%. Test B: Insecticidal action against Heliotheis viretscens Test A above used Heliotheis viretscens larvae in the third larval stage as the test insect,
It was repeated using potted soybean plants as hosts and varying the test compound concentrations to 12.5, 3.0 and 0.75 ppm. Results Compound No. determined by the above tests A and B.
The insecticidal action of ~ is shown in the table below.

[Table] The above results show that test compound No. and is superior in terms of its insecticidal activity compared to compound and which is inactive against the test insects at lower concentrations. Compound No. and
It shows high insecticidal activity against Spotoptera littoralis even at 0.75 ppm, and high insecticidal activity against Heliotheis viretscens even at 3.0 ppm.

Claims (1)

[Claims] Primary formula: (In the formula, R ₂ and R ₃ represent a fluorine atom,
Alternatively, R ₂ and R ₃ represent a chlorine atom, or ₂ represents a fluorine atom or a chlorine atom and R ₃ represents a hydrogen atom. ). Quadratic formula: The compound according to claim 1, which is represented by: Cubic formula: The compound according to claim 1, which is represented by: 4 a) The following formula: A compound represented by the following formula: (In the formula, R ₂ and R ₃ represent a fluorine atom,
Alternatively, R ₂ and R ₃ represent a chlorine atom, or ₂ represents a fluorine atom or a chlorine atom and R ₃ represents a hydrogen atom. ) The following formula is characterized by reacting with a compound represented by: (In the formula, R ₂ and R ₃ have the above meanings.) A method for producing a compound represented by the following. 5 The following formula as the active ingredient: (In the formula, R ₂ and R ₃ represent a fluorine atom,
or R ₂ and R ₃ represent a chlorine atom, or R ₂
represents a fluorine atom or represents a chlorine atom, and R ₃ represents a hydrogen atom. ) together with a suitable carrier and/or other additives. 6. The insecticide according to claim 5 for controlling insects. 7. The insecticide according to claim 6, wherein the insect is a larval stage insect that damages plants.