KR800000248B1 - Process for the preparation of substituted benzoyl ureido-diphenylethers - Google Patents

Abstract

Title compds. (I; R = C1, F, Br, or Me), useful as insecticide, were prepd. by reacting phenoxyaniline(II) with benzoylisocyanate(III). Thus, 2-chlorobenzoylisocyanate 5.5g was dissolved in the toluene 20ml and added to the toluene soln. of 4-(3'-chloro-4'-cyanophenoxy)-3, 5--dichloroaniline at 80≰C. This mixt. was stirred for 1 hr at 60≰C, cooled, filtered, washed with toluene and petroleum ether, and then dried to give 2',3',6'-trichloro-4-cyano-4'-=DN-(N'-(O-chlorobenzoyl))-ureido=E-diphenyl ether 10 g.

Description

Process for preparing substituted benzoyl ureido-diphenyl ethers

The present invention relates to a process for preparing benzoylureido-diphenyl ether of formula (I) which is effective as an insecticide.

In the above structural formula

R is chlorine, fluorine, bromine or methyl.

It is already known that benzoylureas such as N- (2,6-dichlorobenzoyl) -N '-(4-chlorophenyl and -3,4-dichlorophenyl) -urea have pesticidal action. (See German Publication 2,123,236), however, these activities are not satisfactory when used at low concentrations. Surprisingly, however, it has been found that the benzoylureido diphenyl ethers prepared according to the present invention have the most similar structure and exhibit substantially stronger pesticidal activity than the above-mentioned known compounds having the same form of action.

According to the present invention, benzoylureido-diphenyl ethers of formula (I) are prepared by reacting phenoxyaniline of formula (II) with benzoyl isocyanate of formula (III) in the presence of a solvent.

In the above structural formula

R is as described above.

For example, when 4- (3'-chloro-4'-cyanophenoxy) -3,5-dichloro-aniline and 2-chlorobenzoyl isocyanate are used as starting materials, the reaction scheme may be represented as follows.

2-chloro benzoyl isocyanates used as starting materials are known in the literature and other benzoyl isocyanates are generally known in the usual manner (see AJ Speziale et al., J. Org.Chem. It can be prepared according to.

2-fluorobenzamides and other benzamides are known and generally can be prepared according to conventional methods (see Beilsteins Handbuchder Organischen Chemie Vol. 9, p. 336). The phenoxyaniline of formula (II) is prepared according to conventional methods, for example, by the reaction of alkali metal aminophenolates and 1,3-dichloro-4-cyano benzene in a solvent, for example dimethylsulfoxide. can do. (See J. Schramm et al, Justus Liebigs Annalen der Chemie 1970,740,169-179).

Examples of the benzoyl isocyanates (III) used in the present invention include the following compounds. : 2-chloro-, 2-fluoro-, 2-bromo- and 2-methyl-benzoyl are socyanates.

The preparation reaction according to the invention is preferably carried out in the presence of a suitable solvent or diluent. Virtually all inert organic solvents can be used for this purpose, in particular aliphatic and aromatic, optionally chlorinated hydrocarbons such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride, chloro benzene; 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.

The reaction temperature can vary within a very wide range, generally from 0 ° C. to 120 ° C., preferably from 60 ° to 85 ° C.

Generally this reaction takes place under atmospheric pressure.

It is preferable to use an equimolar amount of reactants in carrying out the present reaction. Excessive use of either has no particular advantage.

The compound is obtained in crystalline form with precise melting point.

As already mentioned, the benzoylureido-diphenyl ethers prepared according to the present invention are characterized by excellent insecticidal action, low toxicity to warm-blooded animals and no harm to plants.

For this reason, the compounds can be successfully used as pesticides to protect plants from insects and insects. It can also be used in veterinary medicine.

The pests of which the compounds are useful include the following. Aphids such as peach aphid, soybean aphid, millet rim aphid, pea tree aphid, potato beard aphid, magpie aphid, apple tree dongle aphid, peach aphid, plum aphid; Green worms such as herb beetles, fig beetles, Pseudococcus maritimus, whiskers such as Hercinothrips femoralis, Piesma quadrata, Bugs, such as the Dysdercus intermedius, bedbugs, Rhodnius prolixus, and Triatoma infestans, as well as the cicadas and Eucelis vilo batus. cicadas like bilobatus).

hniella) 및 갈레리아 멜로넬라(Galleria mellonella)가 있다.Insects are particularly Lepidoptera, which include Chinese cabbage moths, straw moths, patterned white moths, tent moths, Chinese cabbage moths, Agrotis segetum, Pieris brassicae, and Camatovia brumatata. (Cheimatobia brumata), Tortrix viridana, Laphygma frugiperda, Tobacco spider moth, Cider moth, Ephestia quiniela

hniella) and Galleria mellonella.

Also classified as coleoptera are coleoptera, weevil, colorado leaf beetle, gastrophysa viridula, flea leaf beetle, melizethes aeneus, byturus tomentosus, soy weevil , Agroceros, tribolium castaneum, sitophilus zeamis, stegobium paniceum, brown rice chops, sawdust chief and living in soil There are Oak leaf scarabs of the genus Agriotes; The wheels include wheels, foreign wheels, madeira wheels, vanilla wheels, Blaberus giganteus, Blaberus fuseus, Henschoutedenia flexivitta; Locusts have house crickets and termites reticulitermes flavipes; There are higher hair ants as logging.

The flies include yellow fruit flies, Cetititis Capitata, house flies, baby flies, Phormia regina, Califora erythrocephala and chimpanzees. There are mosquitoes, such as malaria mosquitoes.

Among the mite are the mite and apple mites, which belong to the mite family, and the mite family has Eriophyes ribis, and the tarsoneamide family has Hemitarsonemus latus and Tarsonemus palidus. pallidus) and ticks include Ornithodorus moubata.

Pests and Stored Pests Harmful to Humans, In particular when using compounds prepared according to the invention in flies or mosquitoes, they are not only long-lasting on wood or clay but also high on alkali.

The compounds according to the invention can be converted into conventional preparations, i.e. solutions, emulsions, suspensions, powders, pasta preparations and granules. It may be prepared according to conventional methods, optionally with surfactants such as emulsifiers and / or dispersants and / or blowing agents. When water is used as a weighting agent, an organic solvent may be used as an auxiliary solvent.

As a liquid diluent or carrier, aromatic hydrocarbons such as xylene, toluene, benzene or alkyl naphthalene, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffin, Alcohols such as butanol and glycol and ethers and esters thereof, acetone and methyl ethyl ketone; Preference is given to ketones such as methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide, dimethyl sulfoxide or acetonitrile or water.

Liquefied gas diluents or carriers are gaseous at room temperature and atmospheric pressure, and include aerosol propellants such as halogenated hydrocarbons (eg Freon).

Preferred solid diluents or carriers are natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as highly dispersed silicic acid, alumina or silicide.

Preferred emulsifiers and foaming agents are nonionic and anionic emulsifiers such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers (alkylaryl polyglycol ethers), alkyl sulfonates, alkylsulfates And arylsulfonates and albumin hydrolysates. Dispersants include lignin sulfite waste liquor and methylcellulose.

The compound may also be used in the preparation as a mixture with other active compounds. In general, formulations contain from 0.1 to 95% by weight, preferably from 0.5 to 90% of active compound.

The active compounds may be used as such or in the form of ready-to-use solutions, suspensions, emulsions, powders, pastas, soluble powders and granules. Moreover, these can be processed by a conventional method, for example, a spraying method, a spraying method, a fumigation method, a smoking method, a spraying method and a powdering method.

The active compound concentration of the ready-to-use formulations can be varied within a very wide range, generally from 0.0001 to 10%, preferably from 0.01 to 1% by weight.

In addition, the present active compound may be produced by the ULV, but it is possible to treat up to 95% of the active compound or the active compound itself.

The pesticidal effect of the compound prepared according to the present invention is illustrated as the following biological test example. All parts herein are by weight unless otherwise indicated.

[Test Example 1]

Faeden Seabed Test

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To obtain a suitable active compound formulation, 1 part by weight of the active compound is mixed with a solvent of this amount containing this amount of emulsifier and diluted with water to the desired concentration.

Cabbage leaves were treated with the active compound preparation until the solution flowed and then infected with Phaedon Cochleariae larvae.

After a certain time, the pesticides were measured in%. 100% indicates that all larvae have been killed and 0% indicates that none have been killed.

Active compound, active compound concentration, measurement time and the results are shown in the following table.

[Test Example 2]

Fludela test

Solvent: 3 parts by weight of dimethyl formamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

The amount of solvent containing the amount of emulsifier is mixed with 1 part by weight of the active compound and diluted with water to the desired concentration to obtain the active compound preparation.

The cabbage leaf was treated with drops of the active compound preparation until it formed a drop and infected with Chinese cabbage moth.

After a certain time, the degree of pesticide was expressed in%. 100% are all killed, 0% is one and not killed.

Active compound, active compound concentration, measurement time and the results are shown in the following table.

[Test Example 3]

Parasitic Fly Larva Test

Solvent: 35 parts by weight of ethylene polyglycol monomethyl ether

Emulsifier: 35 parts by weight of nonylphenol polyglycol ether

30 parts by weight of the active compound were mixed with the above amount of solvent containing the above amount of emulsifier and diluted with water to the desired concentration to obtain the active compound preparation.

About 20 fly larvae (Lucilia cuprina) were placed in a test tube containing about 2 cm 3 of horse breeding and 0.5 ml of the active compound formulation was treated to the horse breeding. Pesticides were measured after 24 hours. 100% indicates that all larvae have been killed, and 0% indicates that no larvae have been killed.

Active compounds, active compound concentrations and the results are shown in the following table.

The following example illustrates the preparation of the compound of formula (I) according to the present invention.

Example 1

A solution of 5.5 g (0.03 mol) of 2-chlorobenzoyl isocyanate in 20 ml toluene was dissolved in 9.4 g (0.03 mol) of 4- (3'-chloro-4'-cyanophenoxy) in 100 ml of toluene. Add dropwise to -3,5-dichloroaniline at 80 ° C. It is stirred at 60 ° C. for 1 hour, cooled and the precipitated product is filtered off and washed first with toluene and then with petroleum ether. 10.0 g of pure 2 ', 3', 6'-trichloro-4-cyano-4 '-[N- (N'-(0-chlorobenzoyl))-ureido] -diphenyl ether having a melting point of 194 DEG C after drying (67%).

Example 2

3.3 g (0.02 mole) of 2-fluorobenzoyl isocyanate solution in 20 mL toluene was added to 6.3 g (0.02 mole) 4- (3'-chloro-4'-cyanophenoxy) in 100 mL toluene. To the -3,5-dichloroaniline solution is added dropwise at 80 ° C. It is stirred at 80 ° C. for 1 hour. The reaction mixture is cooled to 20 ° C. and then the precipitated product is filtered off and washed with toluene and petroleum ether. 2 ', 3', 6'-trichloro-4-cyano-4 '-[N- (N'-(2-fluorobenzoyl))-ureido] at a melting point of 210 캜 after drying = 7 g of diphenyl ether (73%).

According to a method similar to Examples 1 and 2, the following compounds are obtained.

Claims (1)

A process for preparing benzoylureidodiphenyl ether of the following formula (I), characterized by reacting phenoxyaniline of the following formula (II) with benzoylisocyanate of the following formula (III):

In the above structural formula R is chlorine, fluorine, bromine or methyl.