KR800000245B1 - Process for the preparation of benzoil ureido -diphenylethers - Google Patents

Abstract

Benzoylureidodiphenyl ethers (I; R1 = F, Cl, Br or methyl, R2= H, F or Cl, R3 = H or Cl, R4 = H, Cl or methyl, R5 = H or Cl, R6= nitro or trifluoromethyl), useful as insecticides, were prepd. by the reaction of benzoylisocyanates (III) with phenoxyanilines, if necessary, in the presence of diluting agent or solvent, Thus, 3.7 g 2-chlorobenzoyl isocyanate and 5.8 g 4-(2'-chloro-4'-trifluoromethylphenoxy)-aniline were heated in toluene at 80≰C for 1 hr to give I.

Description

Method for producing benzoyl ureido-diphenyl ethers

The present invention relates to a process for preparing benzoyl ureido-diphenyl ethers of formula (I) having strong insecticidal action.

In the above structural formula

R ¹ is fluorine, chlorine, bromine or methyl,

R ² is hydrogen, fluorine or chlorine,

R ³ is hydrogen or chlorine,

R ⁴ is hydrogen, chlorine or methyl,

R ⁵ is hydrogen or chlorine,

R ⁶ represents nitro or trifluoromethyl.

It is already known that benzoylureas, such as N- (2,6-dichlorobenzoyl) -N '-(4-chlorophenyl- and-3,4-dichlorophenyl) -urea, have insecticidal action. (See German Publication No. 2,123,136)

Surprisingly, however, it has been found that benzoylureido-diphenylethers prepared according to the present invention have actually more potent pesticidal activity than the known compounds which have a structure and function almost similar thereto.

Among the benzoylureido diphenyl ethers of formula (I) prepared according to the present invention, R ¹ is chlorine or fluorine, R ² is hydrogen, chlorine or fluorine, R ³ , R ⁴ and R ⁵ are each hydrogen and R ^It is a compound which shows hexavalent trifluoromethyl.

Also preferred are compounds in which R ¹ is chlorine, fluorine or methyl, R ² is hydrogen, chlorine or fluorine, R ³ is hydrogen or chlorine, R ⁴ is hydrogen, R ⁵ is hydrogen or chlorine and R ⁶ is nitro.

More preferred compounds of formula (I) include those in which R ¹ is chlorine, fluorine or bromine, R ² is hydrogen or fluorine, R ³ is hydrogen, R ⁴ is methyl or chlorine, -R ⁵ is hydrogen and R ⁶ is nitro Compound.

According to the present invention, benzoylureidodiphenylether of formula (I) is prepared by reacting phenoxyaniline of formula (II) with benzoyl isocyanate of formula (III) in the presence of a diluent or solvent, if necessary.

(Wherein R ¹ to R ⁶ are the same as described above)

For example, when 4- (2'-chloro-4'-trifluoromethylphenoxy) -aniline and 2-chlorobenzoyl isocyanate are used as starting materials according to the above method, the reaction scheme may be represented as follows.

Benzoyl isocyanates of formula (III) used as starting materials can be prepared according to conventional methods, generally as compounds known in the literature. (AJ Speziale et. Al, J. Org. Chem. 30 (12), 4306- 4307 (1965))

rgen Schramm et. al. Justus Liebigs Annalen der Chemie 1970, 740, 169-179참조)Phenoxyaniline of formula (II) is generally known by methods such as alkali metal aminophenolates and 1,2-dichloro-4-trifluoromethylbenzene or aromatic nitrohalogeno compounds (e.g. 1,2 -Dichloro-4-nitrobenzene) can be obtained by reacting in a solvent such as dimethylsulfoxide.

rgen Schramm et. al. Justus Liebigs Annalen der Chemie 1970, 740, 169-179)

Examples of the benzoylisocyanates of the formula (III) are 2-chloro-, 2-fluoro-, 2-bromo-, 2,6-dichloro- or 2,6-difluoro-benzoylisocyanate.

Examples of the phenoxyaniline of formula (II); 3-chloro-4- (2'-chloro-4'-nitro-phenoxy) -aniline, 3,5-dichloro-4- (2'-chloro-4'-nitro-phenoxy) -aniline and 4- (2'-chloro-4'-nitro-phenoxy) -aniline.

The preparation reaction of benzoylureido diphenyl ethers according to the present invention is preferably carried out in the presence of a suitable solvent or diluent. In practice, all inert solvents can be used, in particular aliphatic and aromatic optionally chlorine-substituted hydrocarbons such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; Ethers such as diethyl ether, dibutyl ether and dioxane; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; Nitriles such as acetonitrile and benzonitrile are suitable.

The reaction temperature can be varied within a very wide range, generally 0 to 120 ° C., preferably 70 to 85 ° C. This reaction generally occurs under atmospheric pressure.

It is preferable to use an equimolar amount of reactants in carrying out the present reaction, and there is no advantage in using an excess of one of the two reactants.

Compounds prepared according to the invention are obtained in crystalline form with sharp melting points.

As already described, the benzoylureidodiphenyl ethers prepared according to the present invention are characterized by excellent insecticidal action and at the same time have low toxicity to warm-blooded animals and high resistance to plants.

For this reason, the compounds can be successfully used for plant protection as insecticides against insects and insects.

Insects are mainly aphids, for example peach or aphid badge border aphids, peaches aphids, potato beard aphids, currant aphids, apple tree round aphids, peach flourish aphids, plum humps and aphids , Shovels, bedbugs and cicada.

Insects include, for example, Chinese cabbage moths, plate moths, patterned white moths, tent moths, Chinese cabbage moths, microseed moths, Chinese cabbage moths, tobacco moths, apple moths, and larvae.

Also included are coleoptera, such as weevils, weevils, creeper leaf beetles, soy weevils, scarabs, brown rice meal, saw blade heads, cockroaches, oak beetles, and wheels as wheels, heterogeneous wheels and maditas. There are wheels, wings, and grasshoppers such as house crickets and fellings such as higher haired ants.

The flies include yellow fruit flies, house flies, baby flies, black flies, chimpanzees, and mosquitoes such as forest mosquitoes, red mosquitoes, and malaria mosquitoes.

The active compounds prepared according to the invention can be prepared from conventional preparations, for example solutions, emulsions, suspensions, powders, pasta preparations and granules. Such formulations are prepared according to conventional methods, for example by obtaining an active compound in combination with a liquid, solid or liquefied gas diluent or carrier and optionally with surfactants such as emulsifiers and / or dispersants, and / or foaming agents. When water is used as a weighting agent, an organic solvent may be used as an adjuvant.

Liquid diluents or carriers include aromatic hydrocarbons such as xylene, tolumen, benzene or alkylnaphthalene, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or mineral oil fraction, Alcohols such as butanol or glycol, or ethers and esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, in addition to water, strong polar solvents such as dimethylformamide, dimethylsulfoxide or acetonitrile desirable.

Liquefied gas diluent or carrier means a liquid that is a gas at normal pressure and room temperature, such as aerosol propellants such as chlorinated hydrocarbons such as freon.

Preferred solid diluents or carriers are natural minerals such as kaolin, clay, talc, whitewood, quartz, attacgit, montmorillonite or diatomaceous earth or synthetic minerals such as highly dispersed silicic acid, alumina or silicate.

Preferred emulsifiers or foaming agents include nonionic and anionic emulsifiers such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, albumin hydrolysates. Lignin, sulfite and methylcellulose.

The active compound according to the present invention can be used in a mixture with other active compounds.

Generally, the effective compound content of the formulation is 0.1 to 95% by weight, preferably 0.5 to 90%.

This effective compound may be used as it is or may be used as a formulation. The method of use is in accordance with conventional methods such as spraying, fumigation, and smearing.

The formulation thus obtained can be diluted in use and the effective compound concentration in use is generally 0.0001 to 10%; Preferably it is 0.01 to 1%.

In addition, the result is good even if it is used by the ultra-low volume method (ULV), and 95% of the active compound can be used as it is (100%).

The pesticidal action of the compounds prepared according to the invention is illustrated by the following bioexperimentation examples.

[Test Example 1]

Flutella test

Solvent: 3 parts dimethylformamide

Emulsifier: 1 part alkylaryl polyglycol ether

One part of the active compound was mixed with the above amount of solvent containing the above amount of emulsifier and diluted with water to the desired concentration to obtain a suitable active compound formulation.

Enbechu (Brassica oleracea) was sprayed with the active compound formulations and then infected with Chinese cabbage moth (Flutella Magnumipennis). After a certain time, the insecticidal activity was measured in%. 100% means that all the moths are dead and 0% means that none of them are dead. Effective compounds, active compound concentrations, measurement times and results are shown in the following table.

TABLE 1

(Insects that harm plants)

Fludela test

[Test Example 2]

Lapigma Exam

Solvent: 3 parts dimethylformamide

Emulsifier: 1 part alkylaryl polyglycol ether

One part of the active compound was mixed with the amount of solvent containing the amount of emulsifier and diluted with water to the desired concentration. Cotton leaves (Gosipium hirsutum) were sprayed with the active compound formulation and then infected with moths of Laphygma exigua.

After a certain time, the insecticidal effect was measured and the results are shown in the following table.

TABLE 2

(Insects that harm plants)

Lapigma Exam

[Test Example 3]

Phaedon Larva Test

Solvent: 3 parts dimethylformamide

Emulsifier: 1 part alkylaryl polyglycol ether

One part of the active compound was mixed with the above amount of solvent containing the above amount of emulsifier and diluted with water to the desired concentration to obtain a suitable active compound formulation.

Cabbage leaves (Brissica oleracea) were sprayed with the active compound formulation until water droplets were formed and then infected with Phaedon Cochleariae.

After a certain time, the insecticidal effect was%: 100% indicates that all the larvae died and 0% indicates that the larvae did not die at all.

Effective compounds, effective compound concentrations, evaluation time and the results are shown in the following table.

TABLE 3

(Insects that harm plants)

Phaedon Larva Test

The present invention is illustrated by the following examples.

Example 1

5.8 g (0.02 mol) of 4- (2'-chloro-4'-trifluoromethylphenoxy dissolved in 100 ml of toluene was dissolved in 3.7 g (0.02 mol) of 2-chlorobenzoyl isocyanate in 120 ml of toluene. ) -Aniline is added dropwise at 80 ° C. It is stirred for 1 hour at 80 ° C., cooled, and the precipitated product is filtered off, washed with toluene and then with petroleum ether. 6.6 g of pure 2-chloro-4-trifluoromethyl-4 '-[N- (N'-(0-chlorobenzoyl) ureido] -diphenyl ether at a melting point of 182 ° C after drying (70% of theory) Get

Example 2

A solution obtained by dissolving 3.7 g (0.02 mol) of 2,6-difluorobenzoyl isocyanate in 200 ml of toluene was dissolved in 5.8 (0.02 mol) of 4- (2'-chloro-4'-trifluoromethyl in 100 ml of toluene. Phenoxy) -aniline was added dropwise at 80 ° C. to the solution. It is stirred at 80 ° C. for 1 hour, cooled to 20 ° C., and the separated material is filtered off, washed with toluene and washed with petroleum ether. 8 g of 2-chloro-4-trifluoromethyl-4 '-[N- (N'-(2,6-difluorobenzoyl) -ureido] -diphenyl ether having a melting point of 187 DEG C after drying. 95%).

Example 3

2-Chloro-4-trifluoromethyl-4 '[N- (N'-2,6 dichlorobenzoyl) -ureido] -diphenyl ether having a melting point of 177 ° C. was obtained in a similar manner as in Examples 1 and 2. Yield: 89% of theory

Example 4

A solution of 2.8 g (0.015 mol) of 2-chlorobenzoyl isocyanate in 10 ml of toluene was dissolved in 5 ml (0.015 mol) of 3,5-dichloro-4- (2'-chloro-4'-nitrophenoxy) in 50 ml of toluene. -Dropwise added to the solution of aniline at 80 ℃. It was stirred at 80 ° C. for 1 hour, cooled, and the precipitated product was filtered off, washed first with toluene, then with petroleum ether and dried to produce pure 2-chloro-4-nitro-2 ', 6'- 6.5 g (84% of theory) of dichloro-4 '-[N- (N'-0-chlorobenzoyl) -ureido] -diphenyl ether are obtained.

Example 5

A solution of 3.25 g (0.02 mol) of 2-methyl-benzoylisocyanate in 20 ml of toluene was dissolved in 80 ml of toluene in 6.0 g (0.02 mol) of 3-chloro-4- (2'-chloro-4'-nitrophenoxy. ) -Aniline was added dropwise at 80 ° C. It is stirred at 80 ° C. for 1 hour and the reaction mixture is cooled to 20 ° C., after which the separated material is filtered off, washed with toluene and washed with petroleum ether. 8 g of 2-chloro-4-nitro-2'-chloro-4 '-[N- (N'-(0-methylbenzoyl))-ureido] -diphenyl ether at a melting point of 220 ° C. after drying (87% of theory) Get)

The following compounds are also obtained according to methods analogous to the above examples.

Example 13

A solution of 3.7 g (0.02 mol) of 2-chlorobenzoyl isocyanate in 20 ml of toluene was dissolved in 500 ml of toluene, 6.0 g (0.02 mol) of 4- (2'-chloro-4'-nitrophenoxy) -2-chloro To the solution of arylene was added dropwise at 30 ° C. and stirred at 50 ° C. for 1 hour. After cooling, the precipitated product is filtered off, washed first with toluene and then with petroleum ether. 6.0 g of theoretically pure 2,3'-dichloro-4-nitro-4 '-[N- (N'-(O-chlorobenzoyl))-ureido] -diphenyl ether having a melting point of 193 DEG C after drying 62%).

Example 14

5.6 g (0.02 mol) of 4- (2'-chloro-4'-nitro-phenoxy) -2-in a solution of 3.7 g (0.02 mol) of 2,6-difluorobenzoyl isocyanate dissolved in 20 ml of toluene Methylaniline was added dropwise at 50 ° C to a solution dissolved in 100 ml of toluene and stirred at 60 ° C for 1 hour. The reaction mixture is cooled to 20 ° C., and then the separated material is filtered off, washed with toluene and petroleum ether. 7 g of 2-chloro-4-nitro-3'-methyl-4 '-[N- (N'-2,6-difluorobenzoyl) -ureido] -diphenyl ether at a melting point of 190 DEG C after drying 75%).

The following compounds are obtained in a similar manner to Examples 13 and 14.

Claims (1)

A process for preparing benzoylureido-diphenyl ether of formula (I), characterized by reacting phenoxyaniline of formula (II) with benzoylisocyanate of formula (III).

In the above structural formula R ¹ is fluorine, chlorine, bromine or methyl, R ² is hydrogen, fluorine or chlorine, R ³ is hydrogen or chlorine, R ⁴ is hydrogen, chlorine or methyl, R ⁵ is hydrogen or chlorine R ⁶ represents nitro or trifluoromethyl.