JPS62207250A - Benzoylphenylurea, manufacture and vermicidal use thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel substituted N-benzoyl-N'-2,s-
The present invention relates to dihalo-4-heroalkoxyphenylureas, methods and intermediates for their production, and methods of using the compounds for pest control.

The compound of the present invention has the following formula:
3 is a mono- or polyhalogenated carbon atom number of 1 to 7
represents an alkyl group, R4 represents a hydrogen atom, a halogen atom, a methyl group, a methoxy group or a methylthio group,
And the turtle 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; fluorine.

Chlorine and bromine atoms are preferred Mono- or polyhalogenated C7-C alkyl groups suitable as substituents can be straight-chain or branched and are only partially halogenated. The substituent may also be perhalogenated, and the halogen atom in the substituent is as mentioned above. Particularly suitable examples of such substituents are, inter alia, 1 to 3 fluorine atoms,
Methyl groups substituted with chlorine atoms and/or bromine atoms 1, e.g. -CHF2 or 10F3: 1 to 5 fluorine atoms, ethyl groups substituted with chlorine and/or bromine atoms, e.g. -CHz CFs , -CF,CF,%
-CF2CC1, -CF,CHCt, .

-CF2CHF2, -CF2CHBr2, -CF2
CHBr2゜-CF2CHBr F or -CCzF
CHCzF; Propyl group or inpropyl Ti each substituted with 1 to 7 fluorine atoms, chlorine atoms and/l or bromine atoms 2 examples L ld'-G(zG(Br
CH2Br, -CF, CHFCF3゜-CHz CF2
CF3 or -CH(CF3); a butyl group substituted with 1 to 9 fluorine, chlorine and/or bromine atoms, or isomers thereof, e.g. Ever CF
(CF3) CHF CFs t 7'c Fi -
CHz (CF2)2 CFs.

Of particular interest are compounds of formula I in which avian and R2 each represent a fluorine, chlorine or bromine atom, provided that R1 and R2 do not simultaneously represent a chlorine atom and R2 is a mono- or polyhalogen. Number of carbon atoms: 1
4 represents an alkyl group, 4 represents a hydrogen atom, a fluorine atom or a chlorine atom, and R5 represents a fluorine atom,
◇Preferred compounds of formula I are those which represent a chlorine atom or a methoxy group, wherein in formula I, 1 represents a fluorine atom and R2 represents a fluorine atom, a chlorine atom or a bromine atom, or R2 represents a fluorine atom, a chlorine atom or a bromine atom; represents a chlorine atom, the island represents a fluorine atom, R3 represents an alkyl group having 1 to 3 carbon atoms substituted with 1 to 7 halogen atoms, R4 represents a hydrogen atom, a fluorine atom or a chlorine atom, and R2 represents a fluorine atom, a chlorine atom or a methoxy group.

Compounds of the formula (3) in which Rt represents a fluorine atom, R2 represents a fluorine atom, a chlorine atom or a bromine atom, and R2 is a group -CHaCF
3. -CCtFCHCtF, -CF2CHBr2.

-CH(CF3), -CH2CF, CF3 or -CFzCHPCFs, R1 represents a hydrogen atom or a fluorine atom, and R2 represents a fluorine atom, a chlorine atom or a methoxy group.

Compounds of the formula (2) which have been singled out for further special mention are those in which R1 represents a fluorine atom, R2 represents a fluorine atom, a chlorine atom or a bromine atom, and R is a group -CHt CFg .

-CH(CF3), -CH, CHFCF3 or -CF2CHFCF3, R4 represents a hydrogen atom or a fluorine atom, and R2 represents a fluorine atom, a chlorine atom or a methoxy group.

Examples of compounds of formula I are, in particular, the following: The compounds of the invention can be prepared by known methods. Such methods are described, inter alia, in DE-A 2.12 to 236, 2,601,780 and 3.240,9.
It is described in the specification of No. 75. Such a compound of formula I may be, for example, a) of the following formula ■: Fan! C) reacting an aniline represented by the formula m with a benzoyl isocyanate of the formula m: or reacting an incyanate represented by the formula V with a benzamide of the formula V; or C) reacting an aniline represented by the formula The following formula ■: □ (In the above formulas ■ to ■, the group R1%, R3, R4 and bird represent the same meaning as defined in formula I, and R is substituted with a haogen atom, preferably a chlorine atom. The above methods aLb) and C) are preferably carried out under normal pressure in the presence of an organic solvent or a diluent. It can be carried out below◇
Examples of suitable solvents or diluents are: ethers and ether-like compounds such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydro-72: N,N-dialkylated carboxamides: aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, xylene, chloroform, [methylene chloride, carbon tetrachloride, and chlorobenzene; nitriles such as acetonidonyl or globionitrile; dimethyl sulfoxide: and keto/1 such as acetone, methyl ethyl ketone, methyl impropyl ketone and methyl isobutyl keto/Oa) method is usually -
10° to +200°C, preferably 0° to 100°C
The process ob) is carried out at 0°C to 150°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 metal or alkaline earth metal, preferably sodium, i.e. the formula ■
For the reaction of the urethane represented by the formula (2) with the aniline represented by the formula (2), the temperature range is preferably from about 60°C to the boiling point of the reaction mixture, and examples of the solvent used include aromatic hydrocarbons, such as ebuluene, xylene, chlorobenzene, etc. and the like are preferred. The starting materials represented by ◎ and V are known and can be prepared by methods analogous to known methods.

The starting material of the formula (1) is a new compound and likewise constitutes an object of the present invention. The compound represented by formula (2) is the following formula (2): R, which is appropriately substituted by a known method.

The carbon nitrobenzene was hydrogenated by a method similar to that described in the Journal of Organic Chem., Vol. 29 (1964), 1 (see also references cited herein). However, anilines of formula (1) can also be prepared by chemical reduction of the corresponding nitro compounds of formula (e.g., stannous chloride/
HCt) can also be obtained by 0 [Houben-Weyl, ”
) Todender Organitschechemy (Meth
Oden d.

org, Chemie) 1 j /1, 422] Another method for preparing anilines of formula 0 is to haloalkylate unacylated or acylated 2,5-dihalo-4-hydroxyanilines and then to The method then consists in removing the acyl group, for example by acid hydrolysis.

The nitro compounds of the formula ■ are also new and constitute the object of the present invention. These compounds include, for example, ti;
- by haloalkylation of dihalo-4-nitrophenol (French patent no. 2.oos, a76 B)
The chemistry of hydroxyl groups (The Chanis
try of the Hydroxyl Group
) 'Pages 83 to 124; Intersci x:, y
, x, (Interscience), New York, 1971] The benzoyl isocyanate represented by @2 is particularly
It can be obtained as follows [Journal Op Agricultural 7-de Chemistry (J,
Agr, Food Chem, ) Volume 21, No. 3
48 and 993: 1973 32 4-haloalkoxyphenyl incanates of formula IV are
A benzamide of formula V used as another starting material can be prepared, for example, by phosgenation of an aniline of formula I by methods commonly used in the art. Well-known (for example, Beilstein)@ha:/doub-
7 Dell Organizer Hemi-(Hand-buc)
h der organischen Chemie
) 'Refer to Vol. 9, page 336) 0 The urethane represented by the formula (■) can be obtained by reacting the benzoyl isocyanate represented by (2) with an appropriate alcohol or by reacting the benzamide represented by the formula (2) or the benzamide represented by the formula (2) by a method known per se. It can be obtained by reaction with the corresponding ester of chloroformic acid Cz-COOR in the presence of a base.

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 warm-blooded animals and plants. .

It is therefore suitable for controlling pests of animals and plants, for example.Such pests mainly belong to the phylum Hypodapoda, for example in particular the order Lepi- doptera.
, Coleoptera , Homoptera (H
omoptera), Heteroptera
ra)% Hymenoptera, Thysanoptera, Orthoptera
Ptera), Anoplura, Flea (8iphonaptera), Piliformes (Anoplura),
Mallo-phaga), Thysan
ura), Isoptera
% P5ocoptera.

or insects of the order Hymenoptera, and arachnids of the order Acarina, such as mites and ticks. It is possible to control all developmental stages of pests, ie adults, insects 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 crops such as fruit and vegetable crops and especially in cotton crops. If the compound is ingested by the adult insects, direct death of the pest or a reduction in egg production and/or elaboration rate is observed. The last-mentioned efficacy is particularly observed in the order Coleoptera. In the control of pests that are parasites of livestock and productive livestock in 1% of animals, the compounds of the invention are particularly useful for ectoparasites 1, such as mites and Ticks and Hymenoptera such as Luciliaser
icata).

formula! 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 are organophosphorus compounds.

Nitrophenols and their derivatives, formamide, urea, carbamates, birethroids.

Chlorinated hydrocarbons and Bacillus thuringiensis (B
aci flus thuringiensis)
◎The compound represented by the formula ■, including the preparation, is in its original form.

or neat emulsions, directly sprayable or dilutable solutions, diluted emulsions, aqueous preparations by known methods, preferably together with the auxiliaries customary in formulation technology.

They are formulated in aqueous solutions, powder tablets, and encapsulates, for example with polymeric substances. The method of application, such as spraying, atomizing, dusting, sprinkling or pouring, as well as the nature of the composition, will depend on the intended audience and environment of use. ) or in combination with other insecticides or acaricides and, where appropriate, solid or liquid auxiliaries. (e.g. by homogeneous mixing and/or milling with a solvent, a solid carrier and, in some cases, a surface-active compound (surfactant)).

Suitable solvents are: aromatic hydrocarbons, preferably moieties having 8 to 12 carbon atoms.

For example 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 or epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water; the solid carriers used for example in dusts and dispersible powders are usually natural mineral fillers such as calcite, Merck , kaolin, montmorillonite or attapulgite to improve physical properties.

It is also possible to add dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated absorbent carriers are of the porous type, eg pumice, crushed/moth.

Seviolite or bethonite; and suitable non-absorbent carriers are materials such as calcite or sand. Furthermore, very large amounts of pregranulated inorganic and organic substances 1%, such as in particular dolomite or pulverized plant debris, can be used.

Depending on the nature of the compound of formula I or its combination with other insecticides or acaricides to be formulated, suitable surface-active compounds include non-ionic, cationic compounds with good emulsifying, dispersing and wetting properties. It is to be understood that the term ◇1 surfactant'', which is a surfactant and/or anionic 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 to 22 carbon atoms).
Alkali metal salts, alkaline earth metal salts, or unsubstituted or! Other suitable surfactants are ammonium salts 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 fatty acid methyltaurate salts as well as modified and unmodified It is also a phospholipid.

However, so-called synthetic surfactants, especially aliphatic sulfonates, aliphatic sulfates.

Sulfonated benzimidazole derivatives or alkylaryl sulfonates are more frequently used; aliphatic sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts; These compounds contain C8-C22 alkyl groups, which also contain the alkyl part of the group, and are, for example, sodium or calcium salts of lignosulfonic acid, dodecyl sulfate or mixtures of fatty alcohol sulfates obtained from natural fatty acids. also includes salts of sulfuric acid esters and salts of sulfonic acids of aliphatic alcohol/ethylene oxide adducts. Sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty acid group containing from 8 to 22 carbon atoms. including. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or the 7talenesulfonic acid/formaldehyde condensation product. The corresponding phosphates, for example 4 to 14 mol of ethylene oxide. Also suitable are salts of phosphoric acid esters of p-nonylphenol adducts, including p-nonylphenol adducts.

The nonionic surfactants are preferably aliphatic or cycloaliphatic alcohols or polyglycol ether derivatives of saturated or unsaturated fatty acids and alkylphenols, which derivatives contain from 3 to 30 glycol ether groups and (aliphatic) 8 to 20 carbon atoms in the hydrocarbon portion and 6 to 18 carbon atoms in the alkyl portion of the alkylphenol.

Other suitable nonionic surfactants are polyethylene oxide and polypropylene glycol.

A water-soluble adduct of ethylene diamino polyglobylene 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 globylene 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 ethers, castor oil thioxylate, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol.

Example of fatty acid ester of polyoxyethylene rubitan, t
Polyoxyethylene norbitane triolate is also a suitable nonionic surfactant.

The cationic surfactants preferably contain as N-substituent at least one C8-C22 alkyl group and as other substituents unsubstituted or halogenated lower alkyl, benzyl or lower hydroΦ The salt is preferably in the form of a halide, methyl sulfate or ethyl sulfate, such as stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethyl ammonium bromitate. be.

Surfactants commonly used in the pharmaceutical industry include, for example, 2'McCutchan's Detergents, which are described in the following publications:
and Emulge Fires Annual (MCCu
tcheon s Detergents and Em
ulsifiers Annual)”, Mac Publishing.

Ridgewood, NJ, 1979; Dr.

Helmut 5tache), @Tensid Ta5hen
buch)', Karl Hansa-7xk Lark (Car
l Hanser Verlag).

Munich and Vienna (1981).

Pest control compositions usually contain a compound of formula I or a combination thereof with other insecticides or acaricides (L1 to 99%, preferably α1 to 95%, solid or liquid adjuvant 1%). 99.9% to 99.9%, and 1 to 25 g of surfactant, preferably 1 to 25 g of surfactant.
Including chi.

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, defoamers,
It may also contain viscosity regulators, binders, tackifiers as well as fertilizers or other active ingredients for special effects.

EXAMPLE Suspend in 22.517f of 88% potassium hydroxide, 120d of dimethyl sulfoxide. 40 gf of trifluoroethanol are added dropwise to this suspension while stirring. Next, while stirring, this solution was mixed with 1 1/2 dimethyl sulfoxide.
Add dropwise to a solution of 9 & 8 g of 2.4-difluoro-5-chloronitrobenzene in 50d at room temperature. Once the addition is complete, the reaction mixture is stirred for an additional 2 hours at room temperature. The reaction mixture was then concentrated and the crude product was dissolved in methylene chloride and
The solution is then washed with water and dried. Finally, the solvent is distilled off. Hexane:ether 10:1 as eluent
The mixture is purified by chromatography through a column of silica gel. Evaporation of the solvent gives the title compound of the following formula: in the form of yellow crystals; mp 54-55°C.

The following compounds were prepared in a similar manner.

1,1.1 Aniso/Aniline The above nitrobenzene 21.59f is dissolved in tetrahydrofuran 220d and hydrogenated for 19 hours at room temperature in the presence of Raney Nickel 41 (H! Absorption: 5.261). The reaction mixture is filtered, the solvent is distilled off and the residue is distilled. The title compound represented by the following formula:
It has a boiling point of LO8 torr and a melting point of 40-41°C.

The following compound was prepared in a similar manner: 2-bromo-4
-amino-5-fluorophenol 28.9 and triethylamine 1.9 at Jl dimethylformamide 15
Put it in 0d. Next, hexafluoropropylene 22.
59? : When introduced at room temperature, the temperature of this batch increases to 50°C. The solvent is subsequently 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 is dried over sodium sulfate and then subjected to fractional distillation to obtain the title compound of the formula: in the form of a pale yellow liquid: boiling point 76-81°C/α001 t.
The following compound was prepared in a similar manner: The final product was a solution of 50 g of 2,6-cyfluorobenzoyl incyanate in 10 g of dry toluene, 50 g of dry toluene.
2-Fluoro-4-(2゜2.2-tIJ7/l/
A solution of 74 g of (oroethoxy)-5-/roroanili is added at room temperature and the batch is stirred for 10 hours. Approximately 75% of the solvent is subsequently removed by rotary evaporation. The precipitate formed was separated by filtration with suction, washed with a small amount of cold toluene and hexane, and dried in vacuo to give the title compound of the following formula: %Formula %:) as a white crystalline powder. Melting point: 201-202°C.

The following compounds were prepared in a similar manner.

Example 2 Example of a formulation of the active ingredient of formula I according to Preparation Example 1.2 (shading throughout is ik%) 2.1. Emulsion stock solution a) b) Compound according to Preparation Example 1.2 10% 25
% castor oil thioxylate 25%
- Cyclohexanone - Butanol 15% - Xylene mixture 65% Ethyl acetate 50% - By diluting this emulsion stock solution with water.

Emulsions of desired concentrations can be obtained.

2.2. Solution Agent a) b) Compound according to Preparation Example 1.2 10 Easy 5
%.

Ethylene glycol monomethyl ethyl - Polyethylene glycol 400 70% - N-methyl-2-pyrrolid 7 20% 20% Epoxidized coconut oil 1% These solutions are suitable for application in microdroplet form.

2. Five grains a) b) Manufacturing practice y11t Compound according to 2 5%
10% Kaolin 94%
-Highly dispersed silicic acid 1
% - attapulgite
90% of the active ingredient is dissolved in methylene chloride, this solution is sprayed onto the carrier and the solvent is subsequently removed under reduced pressure.

2.4. Compound according to Extruded Granule Preparation Example 1.2 10%
Sodium lignosulfonate 2
% carboxymethyl cellulose 1
% Kaolin 8
The 7% active ingredient is mixed and milled with auxiliaries and the mixture is subsequently moistened with water. The mixture is extruded and dried in a stream of air.

2.5. Compound 5 according to Coated Granule Preparation Example 1.2
% polyethylene glycol 200 3%
Kaolin 94
The finely divided active ingredient or formulation is applied homogeneously to the polyethylene glycol-moistened kaolin in a mixer. By this method, a non-dusty, edible granule can be obtained.

2, & Powder a) b) c) d) Compound according to Preparation Example t2 2% 5% 5%
8% Highly dispersed silicic acid 1% 5% --
Talc 97% -95% -
Kaolin -90% -92
By mixing the multiple active ingredients with the carrier and milling this mixture in a suitable mill, a ready-to-use powder is obtained.

λl hydrating agent a) b) c) Compound according to Preparation Example t2 20% 50% 7
5% Lignosulfo 4 Sodium 5%
5% - Sodium lauryl sulfate
3% -5% highly dispersed silicic acid
5% 10 arrogant 10 excellent kaolin
62 Excellent 27% - After thoroughly mixing the active ingredient with all 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.

Compound 40 according to Preparation Example 1.2
% ethylene glycol 1
0qb sodium lignosulfonate
10% carboxymethylcellulose
1% 57% formaldehyde aqueous solution
12% 75% aqueous emulsion silicone oil (18% water
By uniformly mixing 32% of the finely ground active ingredient with auxiliaries and diluting with water, a suspendable concentrate is obtained which allows a suspension of the desired concentration to be obtained.

C8MA nutrient medium sag against freshly prepared maggots
fill the beaker. Pipette 5 d of an acetone solution containing 1% by weight of the test compound 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 turned into spiders, the jyo is separated by washing it out of the medium with water and placed in a container closed with a lid with holes.

This is done by counting each batch of dance that is poured out and the growth of maggots.

In this test the compound according to Example 1.2 showed a good effect.

Aqueous formulation 1d containing α5% of the test compound is added to 9 m of nutrient medium at 50°C. Approximately 30 new trout-formed Lucilia cercata larvae are then added to the nutrient medium and the insecticidal effect is determined by assessing mortality after 48 and 96 hours.

In this test, the compound according to Example 1.2 was Lucilia
It showed good action against Cercata.

55 Egyptian Yap Mosquito (A es aegypti)
Effect on the surface of 150 d of water in a beaker, 11% of the test compound
12.5 by pipetting a certain amount of acetone solution.
A solution with a concentration of ppm is obtained. % after acetone evaporates
Thirty to forty 2-day-old Egyptian Yap mosquito larvae are placed 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.

54. Insecticidal action against feeding insects. 100% of the test compound was applied to each plant (approximately 20cm tall).
An aqueous emulsion (prepared from a 10 kettle emulsion stock solution) containing a concentration of ppm is sprayed. After the spray coating has dried, apply 5podoptera littoralis (5podoptera 1it).
toralis) and He1iothis virescens (OI)
, stage larvae to inhabit cotton plants. The test was conducted at 24°C.
Perform at 60% relative humidity. After 24 hours, a mortality count is taken and the inhibition of larval development and molting is also checked.

In this test the compound according to Example 1.2 showed a good effect.

5 about 15 to 20 feet tall grown in a pot
Cotton plants are each treated with a sprayable liquid formulation of the test compound. After the spray coating dries, pot plants about 201! into a metal container with a capacity of i and cover with a glass plate. Adjust the humidity in the covered container to avoid the formation of condensed water! It has been illicit. Avoid direct light hitting the plant. All five plants are then a) Subodoptera littoralis or Heliothis virescens L! 50 stage larvae; b) 2 L3 stage larvae of Subodoptera littoralis or Heliothis virescens;
0 C) Infect with 2 eggs deposits of Subodoptera littoralis or Heliothis virescens.

(The procedure is to place each plant in a plexiglass cleft cylinder closed at both ends with two leaves.

(Addition of two Subodoptera egg deposits or a portion of a cotton leaf on which Heliothis eggs have been deposited to a leaf sealed in a cylinder) Comparison with an untreated control was evaluated. , 4
to 5 days later, according to the following criteria.

a) Number of larvae still alive b) Inhibition of larval development and development C) Eating (breakage and perforation damage) d) Pilling rate (number of larvae that formed from eggs) In this test, The compound according to Example 1.2 is 4 (] Q
It shows a good killing effect at a concentration of ppm.

5 & Killing of Subodoptera littoralis - Egg-pulling - 1. Cut the eggs of Subodoptera littoralis accumulated on a paper, and then incubate the α05-fold I! ：Immerse in % solution. The treated pile was then removed from this mixture and heated to 28°C.
and keep it in a plastic dish at 60% humidity. The 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.

A pile of Lasbeiresia bomonella eggs aJ within 24 hours after spawning is immersed on a piece of paper for 1 minute in an acetone solution containing 2 aooppm of the test compound.

After the solution has dried, place one egg in a vetri dish and keep at a temperature of 28°C. After 6 days, 6 of the larvae that had turned into trout from the treated rabbits.
Find the fraction.

The compound according to Example 1.2 showed good efficacy in this test.

Adults of Annnomus grandis within 24 hours after becoming a town are transferred into closed cages in groups of 25 individuals. The cage is then immersed for 5 to 10 seconds in an acetone solution containing α1% by weight of the test compound. Once the beetles are dry, they are placed in a dish with a canopy containing food and left for mating and spawning.

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 5 hours, and then placed in a dish containing appropriate larval food. To determine whether the larvae have matured from eggs, count the ex of larvae after 78 years.

The persistence of the reproductive inhibitory effect of the test compound is determined by weighing the egg deposits over a period of about 4 weeks. The evaluation is made by the reduction in the number of eggs and displaced larvae compared to the untreated control group.

In this test the compound according to Example 1.2 was.

Shows good reproductive suppression effect.

Test compound i was applied to two six-leaf stage cotton plants in pots.
A hydratable emulsion containing a concentration of 100 ppm is completely sprayed. After the sprayed cover has dried (approximately 114 spots), each plant is populated with 10 adult beetles (Annnomus 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 are kept at 25°C and 60% relative humidity. The evaluation is carried out by examining the mortality rate (% dorsal position) of the beetles and the anti-feeding effect compared with the untreated control group after 2.3° 4 and 5 days.

In this test the compound according to Example t2 showed good efficacy.

-niyuCL -79-,<z-',/5z)-1f
ybshi (Epilach--na varivesti)
s ) for a working height of 15 to 20! Phaseolus vulgari (Phaseolus vulgari)
s) 800 for plants (dwar phloem S)
An aqueous emulsion of the test compound at a concentration of ppm is sprayed.

After the sprayed coating has dried, each plant is populated with five Mexican beanbeetle L4 stage larvae. Immediately cover the treated plants with a plastic cylinder and cover the top with a copper screen. The test is conducted at 28° C. and 60% relative humidity. Mortality is determined after 2 and 3 days. The insects in this test are observed for an additional 6 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.

An equivalent amount of a hydrating powder containing 25% by weight of the test compound for
Mix with sufficient water to produce an aqueous emulsion with an active ingredient concentration of 0.00 ppm. Deposits of one-day-old eggs of Heliothis on cellophane and one-day-old eggs of Subodoptera on paper are immersed in these emulsions for 3 minutes and then collected by suction in a circular filter. The treated pile is placed in a bedding dish and kept in the dark at 28° C. and 60% relative humidity.

The exclusion 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 shows an ovicidal effect (mortality rate) of 80 to 100 in a single test.

A12. Effect on Lasbeiresia pomonella (eggs) K A deposit of Lasbeiresia Bomonella eggs within 24 hours after spawning is immersed on T-paper for 1 minute in an acetone solution containing 800 ppm of the test compound.

After the solution has dried, the eggs are placed in a vetri dish and kept at a temperature of 28°C. After 6 days, the percentage of larvae that have matured from the treated eggs and the mortality rate are determined.

The compound according to Example 1.2 shows good efficacy in this test.

Claims (51)

[Claims] (1) The following formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (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, and R_3 represents a mono- or polyhalogenated C1-C7 alkyl group, 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; A compound represented by (representing a group). (2) In the above formula I, 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, R_3 represents a mono- or polyhalogenated alkyl group having 1 to 4 carbon atoms, R_4 represents a hydrogen atom, a fluorine atom or a chlorine atom, and R_5 represents a fluorine atom, The compound according to claim 1, which represents a chlorine atom or a methoxy group. (3) In the above formula I, R_1 represents a fluorine atom, and R_2 represents a fluorine atom, chlorine atom, or bromine atom, or R_1 represents a chlorine atom, R_2 represents a fluorine atom, and R_3 represents 1 or 2. a C1-C3 alkyl group substituted with 7 halogen atoms, R_4 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; A compound according to scope 2. (4) In the above formula I, R_1 represents a fluorine atom, R_2 represents a fluorine atom, a chlorine atom, or a bromine atom, and R_3 represents a group -CH_2CF_3, -CClFCHCl
F, -CF_2CHBr_3, -CH(CF_3)_2
, -CH_2CF_2CF_3 or -CF_2CHF
4. The compound according to claim 3, wherein CF_3 represents a hydrogen atom or a fluorine atom, and R_5 represents a fluorine atom, a chlorine atom, or a methoxy group. (5) In the above formula I, R_3 is a group -CH_2CF_3,
-CH(CF_3)_2, -CH_2CF_2CF_3
or -CF_2CHFCF_3. The compound according to claim 4. (6) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (7) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (8) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (9) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (10) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (11) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (12) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (13) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (14) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (15) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (16) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 2, which is represented by: (17) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 2, which is represented by: (18) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: (19) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (20) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (21) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (22) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (23) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (24) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (25) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (26) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (27) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 5, which is represented by: (28)a) The following formula II: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) Aniline represented by the following formula III: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) or b) isocyanate represented by the following formula IV: ▲Mathematical formulas, chemical formulas, tables, etc.▼(IV) is converted into benzamides represented by the following formula V: ▲Mathematical formulas, chemical formulas, tables, etc.▼(V) or c) react the aniline represented by formula II with the following formula VI: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VI) (In the above formulas II to VI, each of R_1 and R_2 represents a halogen atom. However, R_1 and R_2 do not simultaneously represent a chlorine atom, and R_3 represents a mono- or polyhalogenated alkyl group having 1 to 7 carbon atoms,
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, and R has a carbon atom number of 1 which may be halogenated.
Represents 8 to 8 alkyl groups. ) The following formula I consists of reacting with urethane represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)
has the same meaning as above. ) A method for producing a compound represented by (29) In the above formula I, 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, R_3
represents a mono- or polyhalogenated C1-C4 alkyl group, R_4 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 manufacturing method according to scope item 28. (30) At least one type of the following formula I as an active ingredient: ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R_1 and R_2 each represent a halogen atom, but R_1 and R_2 do not represent a chlorine atom at the same time, and R_3 is a mono- or polyhalogenated carbon atom. represents an alkyl group of numbers 1 to 7, 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. A pest control agent containing a compound together with a suitable carrier and/or auxiliary agent. (31) In the above formula I, 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 a chlorine atom at the same time, R_3
represents a mono- or polyhalogenated C1-C4 alkyl group, R_4 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 pest control agent according to claim 30, which contains as an active ingredient. (32) In the above formula I, 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 an alkyl group having 1 to 3 carbon atoms substituted with 1 to 7 halogen atoms, R_4 represents a hydrogen atom, a fluorine atom or a chlorine atom, and R_5 represents a fluorine atom, 32. The pest control agent according to claim 31, which contains at least one compound representing a chlorine atom or a methoxy group as an active ingredient. (33) In the above formula I, R_1 represents a fluorine atom, R_2 represents a fluorine atom, a chlorine atom, or a bromine atom, and R_3 represents a group -CH_2CF_3, -CClFCHC
IF, -CF_2CHBr_2, -CH(CF_3)_
2, -CH_2CF_2CF_3 or -CF_2CH
The pest control agent according to claim 32, which contains as an active ingredient at least one compound which represents FCF_3, R_4 represents a hydrogen atom or a fluorine atom, and R_5 represents a fluorine atom, a chlorine atom, or a methoxy group. . (34) In the above formula I, R_3 is a group -CH_2CF_3
, -CH(CF_3)_2, -CH_2CF_2CF_
34. The pest control agent according to claim 33, which contains at least one compound representing -CF_2CHFCF_3 or -CF_2CHFCF_3 as an active ingredient. (35) The following formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (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, and R_3 represents a mono- or polyhalogenated C1-C7 alkyl group, 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; A method of using a compound represented by (representing a group) for controlling pests of animals and plants. (36) Formula I for controlling insects and arachnids
36. The method according to claim 35, which uses a compound represented by: (37) formula for controlling plant-damaging insects in the larval stage
Claim 3 using the compound represented by I
The method described in Section 6. (38) Pests of animals and plants at their various stages of development are expressed by the following formula: However, R_1 and R_2 do not represent a chlorine atom at the same time, R_3 represents a mono- or polyhalogenated alkyl group having 1 to 7 carbon atoms, 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. (39) The following formula VII: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VII) (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, and R_3 a mono- or polyhalogenated C1-C7 alkyl group). (40) In the above formula VII, each of R_1 and R_2 represents a fluorine atom, a chlorine atom or a bromine atom, provided that R
40. A compound according to claim 39, wherein_1 and R_2 do not simultaneously represent a chlorine atom and R_3 represents a mono- or polyhalogenated C1 -C4 alkyl group. (41) In the above formula VII, 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
41. A compound according to claim 40, wherein represents a fluorine atom and R_3 represents a C1-C3 alkyl group substituted with 1 to 7 halogen atoms. (42) In the above formula VII, R_1 represents a fluorine atom, R_2 represents a fluorine atom, chlorine atom or bromine atom, and R_3 is a group -CH_2CF_3, -CClC
HClF, -CF_2CHBr_2, -CH(CF_3
)_2, -CH_2CF_2CF_3 or -CF_2
42. A compound according to claim 41 representing CHFCF_3. (43) In the above formula VII, R_3 is a group -CH_2CF_3
, -CH(CF_3)_2, -CH_2CF_2CF_
3 or -CF_2CHFCF_3. (44) The following formula II: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (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, and R_3 a mono- or polyhalogenated C1-C7 alkyl group). (45) In the above formula II, 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
45. A compound according to claim 44, wherein _3 represents a mono- or polyhalogenated C1-C4 alkyl group. (46) In the above formula II, 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 1 46. The compound according to claim 45, which represents an alkyl group having 1 to 3 carbon atoms substituted with 7 to 7 halogen atoms. (47) In the above formula II, R_1 represents a fluorine atom, R_2 represents a fluorine atom, chlorine atom or bromine atom, and R_3 is a group -CH_2CF_3, -CClFC
HClF, -CF_2CHBr_2, -CH(CF_3
)_2, -CH_2CF_2CF_3 or -CF_2
47. A compound according to claim 46 representing CHFCF_3. (48) In the above formula II, R_3 is a group -CH_2CF_3,
-CH(CF_3)_2, -CH_2CF_2CF_3
or -CF_2CHFCF_3. The compound according to claim 47. (49) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 48, which is represented by: (50) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 48, which is represented by: (51) The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 48, which is represented by: