KR820002081B1 - Process for preparing novel substituted n-phenyl-n'-benzoyl-ureas - Google Patents

Abstract

The title compds. (I; R=C1-4 halogenoalkyl; R1=H, halogen; R2=halogen, nitro, C1-3 alkyl or alkoxy; X=O, S; n=0-5), useful as insecticides, were prepd. by the reaction of II and III. Thus, 50.8g trifluoromethoxyphenylisocyanate in toluene was treated with 38.9g 2-chlorobenzamide in toluene and the mixt. stirred 3.5hr at 105≰C to give 73.6g N-(4-trifluoromethyoxyphenyl)-N'-(2-chlorobenzoyl)-urea(m.p. 196≰C).

Description

Method for preparing newly substituted N-phenyl-N'-benzoyl-urea

The present invention relates to a method for preparing N-phenyl-N'-benzoyl urea of the general formula (I) having strong insecticidal action.

In the above general formula

R is halogenoalkyl having 1 to 4 carbon atoms,

R ¹ is hydrogen or halogen,

R ² is halogen, nitro, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms.

X is an oxygen atom or a sulfur atom,

n is 0,1,2,3,4 or 5.

Preferably

R is straight or branched chain halogeno alkyl having 1 to 3 (particularly 1 or 2) carbon atoms,

R ¹ is hydrogen or chlorine,

R ² is nitro, fluorine, chlorine, bromine, iodine, methyl, ethyl, methoxy or ethoxy,

n is 0, 1, 2 or 3.

It is already known that benzoyl ureas such as N- (2,6-dichlorobenzoyl) -N '-(4-chloro- or 3,4-dichloro-phenyl) -urea have pesticidal action. (Reference: German Publication 2,123,236)

However, the present invention relates to a new class of benzoyl compounds useful as insecticides.

N-phenyl-N'-benzoyl-urea of the general formula (I) of the present invention is substituted with a substituted wasteyl isocyanate of the general formula (II) to benzamide of the following general formula (III) with a suitable diluent or solvent It is made by reacting under.

In the above general formula

R, R ¹ , R ² , x and n are as defined above.

N-phenyl-N'-benzoyl urea according to the present invention has stronger insecticidal action than a compound having a similar structure. Thus, the compounds according to the invention are those compounds in which the art of the art is advanced.

When 3-chloro-4-trifluoromethoxy phenyl isocyanate and 2,6-difluoro benzamide are used as starting materials, the reaction route can be represented by the following formula.

The amino group is converted to an isocyanate group by reaction with a phosgene in a conventional process, and commercially available phenyl isocyanate (II) is obtained. For example:

4-trifluoromethoxy-, 4-trifluoro methylthio-, 3-trifluoromethoxy-, 3-trifluoromethylthio, -2-trifluoromethoxy-2-trifluoromethyl-thio- , 3-chloro-4-trifluoromethoxy-, 3-chloro-4-trifluoromethylthio, 4-difluoro monochloromethylthio, 3-chloro-4-difluoromonochloromethylthio-, 2-chloro-4-difluoromonochloromethylthio-, 4- (2-chloro-1,1,2-trifluoro-ethoxy)-and 3-chloro-4- (2-chloro-1, 1,2-trifluoro-ethoxy-phenyl isocyanates.

Benzamides (III) used as starting materials are known compounds.

(Creation Beilsin "Hand buch der organischen Chemie" ("Hand book of organic Chemistry") Volume 9, page 336).

For example:

2-methyl, 2-ethyl-, 3-methyl, 3-ethyl, 4-methyl-, 4-ethyl-, 2-chloro, 4-chloro-, 2,4-dichloro-, 2,4-difluoro -2,6-dichloro-, 2,6-difluoro-, 2-fluoro-, 2-bromo-, 2-iodo-, 2-nitro-, 3-nitro, 4-nitro,- 2methoxy-, 2-ethoxy- and 2,3,6-trichloro-benzamides.

N-phenyl-N'-benzoyl-ureas according to the invention are preferably prepared in the presence of suitable solvents or diluents and practically all inert organic solvents, in particular aliphatic and aromatic, optionally chlorinated hydrocarbons (e.g. benzene, toluene, Xylene, benzine, methylene chloride, chloroform, carbon tetra, chloride and chlorobenzene), ethers (e.g. dimethyl ether, dibutyl ether and dioxane), ketones (e.g. acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl Isobutyl ketone nitriles (eg, acetonitrile and propionitrile) can be used.

The reaction temperature can be varied over a wide range of temperatures but in general the reaction is carried out at 0 ° C. to 120 ° C., preferably at 70 ° C. to 85 ° C. and the reaction generally takes place under normal pressure.

It is preferable to use equimolar amounts of the starting component to perform the affirmation, and there is no practical benefit in using an excess of one reactant.

In general, the reaction uses one of the solvents described above, and the substituted phenyl isocyanate (II) used in the production process can be used in the form of a reaction mixture obtained after the reaction of the amine with phosgene without intermediate separation. Preferably benzamide (III) is added to the reaction mixture containing one of the solvents described above. The reaction is usually carried out under the conditions mentioned above and the product is separated, washed with filtration and recrystallized as necessary. The compound is obtained in crystalline form with the correct melting point. As already mentioned, the N-phenyl-N'-benzoyl ureas according to the present invention exhibit excellent pesticidal action and are effective against plant pests as well as in the field of veterinary medicine, such as parasitic butterfly larvae (external parasites). Also valid for. For this reason, the compounds according to the invention are effectively used as insecticides in the field of plant protection and livestock. The active compounds are resistant to plants and have low toxicity to warm-blooded animals and are used for storage pool protection and sanitation as well as for the eradication of insect pests, particularly farmland and forest insects. The compounds are generally active against sensitive and resistant species and also against pests of all growth stages.

The pests mentioned above are as follows.

Isopoda river, for example Oniscus asellus, Armadil-lidium vulgare, Porscellio scaber river, Dilopoda Braniulus guttalatus; Chilopoda rivers such as Geophilus Carrpophagus and Scutigera species;

The Symmphla river, for example Scutigerella immaculata; Thysanura, for example Lepisma sucghariua; Collembola, for example Onychiurus armatus, Orthoptera, for example, Blata orientalis, Achetaamoricane, Leucopaea madeera (Leucophaea maderae), wheels (Blattella germanica), Akeda domesticus, Gryllotapa spp, Locusta migratorid migratoride, Melanopus differentialus and Melstoplus differentials Gregaria (Schistocerca giegaria)

Orrmaptera, for example Porpicura auriculara termite (Lsoptera), for example Reticulitermes spp;

Anoplura, for example, Phylloxera vastatrix, Pemphigus spp, Pedicurus humanus corporis, Haematopinus spp;

Linognathus spp Mallophaga includes, for example, Trichodectes spp and Damarinea spp;

) 갈레리아 멜로넬라(Galleria mellonella), 임말이나방(Cacoecia podana), 케푸아 레티쿠라나(Capua reticulana), 코리스토네우라 푸미페라나(Choristoueura fumiferna), 크리시아 암비구엘라(Clysia ambiguella), 호모나 아그나니마(Homona magnaanima) 및 호르트릭스 비리다나(Tortrix viridana) 딱정벌레목(Coleoptera)에는, 예를들면 아노비움 푼크타럼(Anobium punctatum), 라이조페트라 도미니카(dominica Rhizopertha), 브루키디우스 오브레크투스(Bruchidius obtectus), 아켄토스세리데스 오브테크터스(Acanthoscelides obtectus) 히로투루페스 바주루스(Hylotrupes bajulus), 아게라스티카 알니(Agelastica alni), 네프티노타르사 데셈리네아타(Leptinotarsa decemlineata) 파에돈 코프레아리아에(Phaedon cochlecriae), 디아브로티카 아종(Diabrotica spp), 프실리오데스 크리소세파라(Psylliodes crysocephala), 에피라크나 바리베스테스(Epilachna varivestis), 아토마리아 아종(Atomaria spp), 톱날머리 대장(oryzaephilus surinamerisis), 안토노머스 아종(Anthonomus spp), 시토피루스 아종(Sitophilus spp), 오티오르흰커스 술카투스(Otiorrhynchis salcatus), 코스모포리테스 소르디두스(cosmopolites sordidus), 세우보르흰커스 아씨밀리스(ceuthorrhynchus assimilis), 히페라 포스티카(Hypera postica), 데르메스테스 아종(Dermestes spp) 트로고데르마 아종(Trogoderma spp), 안스레누스 아종(Anthrenus spp), 아타게누스(Attgenus spp), 리크투스 아종(Lyctus spp), 메르케테스 아에네우스(Meligarthes aeneus), 프티누스 아종(Ptinus spp), 니푸루스 호로레우커스(Niptus hololeucus), 기비움 피슬로이데스(Gibbium pyslloides), 트로보리움 아종(Tribolium spp), 테네브리오 모리토르(Tenebrio molitor), 아그리오테스 아종(Agriotes spp), 코노데루스 아종(Conoderus spp), 메로론타 메로론타(Melolontha melolontha), 암피말론 솔스티티아리스(Amphimallon solstitialis) 및 코스테리트라 제아란디카(Costelytra zealandia);Thysanoptera includes, for example, Hercinothrips femoralis and Thrips tabaci; Heteroptera includes, for example, Eurygaster spp, Dysdercus intermedius, Piesma guadrata, Cimex Lectularius, Rodnius Pr. Rhodnius Prolixus, and Triatoma spp Homoptera include, for example, Aleurodes brussicae, Bemisia tabaci, Triareurodes vaporariorum (Trialeurodes vaporariorum), Apis gossypii, Brevicoryne brassicae, Cryptomyzus rivis, Doralis fabae, Doralis pomi, Apple worm (Eriosoma lanigerum), Peach aphid (Hyalopterus arundinis), bearded aphid (Macrosiphnm avenae), mythic aphid subspecies (Myzus spp), Euscelis bilobatus, Nephhotic ticobacillus (Nephotittix ci) ncticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilapparvata lugens, Aonidiella aurantii , Aspidiotus hederae, Pseud ococcus spp, and Psylla spp; Lepidopetera includes, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrphoea, Lymantria spp, Bracculatrix thurberiella Phyllocnistis citrella, Agrotis spp, Euxoa spp Feltia spp, Earias insulana, Heliothis spp Rapigma exisigua (Laphygma exigua), Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp, Tricopuru Trioplusiani, Carpocapsa pomonella, Pieris spp, Chilo spp, Pyrausta nubilalis Ephestia Ephestia

Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoueura fumiferna, Clysia ambiguella, Homona Homona magnaanima and Tortrix viridana Coleoptera include, for example, Anobium punctatum, dominica Rhizopertha, Bruchidius obrectus Bruchidius obtectus, Acanthoscelides obtectus Hilotrupes bajulus, Agelastica alni, Nephtinotarsa desemrineata (Leptinotarsa decemlineata) Phaedon cochlecriae, Diabrotica spp, Psylliodes crysocephala, Epiracna varivestis, Atomaria spp, sawy cape (oryzaephilus surinamerisis), anthonusmus spp, Sitophilus spp, Otiorrhynchis salcatus, cosmomorphite sordi Cosmopolites sordidus, ceuthorrhynchus assimilis, Hypera postica, Dermestes spp Trodederma spp, Anthrenus subspecies spp, Attgenus spp, Lyctus spp, Mercethes aeneus, Ptinus spp, Niprus hololeucus, Gambium Gibbium pyslloides, Tribolium spp, Tenebrio molitor, Agriotes spp, Conoderus spp, Melonta Melonta melolontha), Amphimalon Amphimallon solstitialis and Costeritra zealandia;

Hymenoptera includes, for example, Diprion spp, Hoplocampa spp, Homocampa spp, Lasius spp, Monomorium pharaonis and Vespa spp. )

Dipteria includes, for example, Aedes spp, Anopheles spp, Curex spp, Dorosophila melanogaster, Housefly subspecies (musca spp), and baby housefly. Subspecies (Fannia spp), Califora erythrocephala, Lucilia spp, Chrysomyia spp, Cuterebra spp, Gastrophilus spp. ) Hypopobosca spp, Stomoxys spp, oestrus spp Hypoderma spp, Tabanus spp, Tanania spp , Bibio hortulanus, Oscinela frit, Forbia spp, Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipra Farudosa (T ipula paludosa);

In Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp.

Active compounds include liquids, emulsions, wet powders, suspensions, powders, sprays, foaming agents, pasta preparations, melted powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and Conventional formulations such as synthetics, polymers for seed treatment and fine capsules in coating compositions, formulations used with plasticizers such as fumigation cartridges, fumigation cans, fumigation coils, as well as ULV cooling and warming formulations Can be.

These formulations are prepared by known methods, e.g., extenders which are liquid or solid or liquefied gas diluents or carriers and the active compounds are mixed and optionally used together with surfactants which are emulsifiers and / or dispersants and / or foaming agents.

When water is used as the extender, the organic solvent can be used as a cosolvent.

As a liquid diluent or carrier, aromatic hydrocarbons such as xylene, toluene, benzene or alkyl nattalene, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexane or paraffins (mineral oil fraction) and Alcohols such as aliphatic hydrocarbons, butanol or glycol and these ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone or strong polar solvents such as dimethylformamide, dimethyl sulfoxide or acetonitrile Is preferably used.

Liquefied gas diluents or carriers are liquids which become gases at temperature and normal pressure. For example aerosol propellants, such as halogenated hydrocarbons, for example freons.

As solid diluents or carriers, natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or synthetic minerals such as well-dispersed silicic acid, alumina or silicate are preferably used.

Emulsifiers and foaming agents include polyoxyethylene fatty acid esters, polyoxyethylene-fatty alcohol ethers such as alkyl arylpolyglycol ethers, alkylsulfonates, alkylsulfates and arylsulfonates and albumin hydrolysis products. The same nonionic and anionic emulsions are preferred and preferred as dispersants are lignin sulfite waste and methylcellulose. Carboxymethyl cellulose and powder. Formulations such as natural or synthetic polymers (eg gum arabic, polyvinyl alcohol and polyvinyl acetate) in the form of granules or latiss can be used. For example, inorganic dyes such as iron oxides, titanium oxides and purplish blue, and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace elements such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc It can be used as a colorant.

The formulations generally comprise from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90% by weight.

The active compounds according to the invention can be in the form of commercially available formulations or in the form of uses prepared from such formulations. The active compound content of the use form prepared in the form of a commercially available solvent can be varied in a wide range. The active compound concentration is 0.0000001-100% by weight of the active compound, preferably 0.01 to 10% by weight.

The compounds can be used in special use forms by conventional methods. In the field of veterinary medicine, the active compounds according to the invention can be administered orally (e.g. tablets, capsules, drenches, or granules) or used on the skin (e.g. dipping, spraying, pouring, applying drops and powders). And parenteral administration (eg injection).

The present invention uses insecticides, in particular insecticidal and mixed with solid or liquefied gas diluents or carriers or mixed with liquid diluents or carriers containing surfactants.

The present invention also provides a method for eradicating the compound of the present invention alone or in the form of a composition mixed with a diluent or carrier, for use in a beetle, in particular a pest or habitat thereof.

The present invention may also be used in the field before or during the crop growth and / or in combination with a diluent or carrier to protect the crops damaged by the beetle and enhance the crop harvest according to the present invention.

The pesticidal action of the present invention is illustrated by the following biological test examples and the active compounds of the present invention are given the same number of corresponding preparation examples.

Example A

Phaedon Larva Test

Solvent: Dimethylformamide 15 parts by weight

Emulsifier: Alkyl aryl polyglycol ether 1 part by weight

To incorporate the active compound into a suitable formulation, 1 part by weight of the active compound is mixed with the above amount of emulsifier and solvent and diluted with water to the desired concentration. Cabbage leaves (Brassica deracea) are sprayed with an active compound preparation until soaked and then infected with mustard worm larvae (phaedon cochleariae). After the test, the lethality is determined as a percentage.

100% of all the beetle larvae are dead and 0% of the beetle larvae are dead.

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

Table (A) Pests that damage plants

Phaedon Larva Test

Example B

Flutella test

Solvent: Dimethylformamide 15 parts by weight

Emulsifier: alkylaryl polyglycol ether 1 part by weight

To make the active compound into a suitable formulation 1 part by weight of the active compound is mixed with the above amount of emulsifier and solvent and diluted with water to the desired concentration.

Cabbage leaves (Brossica oleracea) are sprayed with an active compound until soaked and then infected with the plutella maculi pennis caterpillar.

After the test, the lethality is determined as a percentage. 100% of all caterpillars are dead and 0% of all caterpillars are dead. Active compounds, active compound concentration measurement time and results are shown in the following table.

TABLE B (Plant Damage Pest)

Flutella test

Example C

Laphygma test

Solvent: Dimethylformamide 15 parts by weight

Emulsifier: alkylaryl polyglycol ether 1 part by weight

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

Cotton leaf (Gossypium hirsutum) is sprayed with an active compound preparation until soaked and then infected with caterpillars of Laphrgma exiqua.

After the test, the lethality is determined in%.

100% of all caterpillars are dead and 0% of all caterpillars are dead.

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

TABLE C (damaged plant pests)

Lapigda Exam

Example D

Parasitic Butterfly Larva Test

Solvent: Erylene polyglycol, 35 parts by weight of monomethyl ether, 35 parts by weight of nonylphenol polyglycol ether

To make the active compound into a suitable formulation, 30 parts by weight of the active substance are mixed with the above amount of emulsifier and solvent and diluted with water to the desired concentration.

30 to 50 butterfly oil layers (Lucilia cuprina, resistant) are placed in a test tube containing 1 cm 3 of horse meat and 0.5 ml of the active compound preparation is added thereto. After 24 hours the lethality is determined in%. 100% of all larvae are dead and 0% of all larvae are dead.

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

TABLE D

Parasitic Butterfly Larva Test

The process of the present invention is described as the following production examples.

The process of the present invention is described as the following production examples.

Example 1

A solution of 50.8 g (0.25 mol) of trifluoromethoxyphenyl isocyanate in 100 ml of toluene is added to a solution of 38.9 g (0.25 mol) of 2-chlorobenzamide in 500 ml of toluene at 100 ° C. The batch is stirred at 105 ° C. for 3 hours 30 minutes and then cooled to 30 ° C. The precipitated product was filtered off, washed with cooled toluene and dried to 76.3 g (85% of theory) of N- (4-trifluoro methoxyphenyl) -N '-(2-chlorobenzoyl) -urea To obtain. Melting Point 196 ℃

All other compounds described in the table are obtained in a similar manner.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

TABLE 6

TABLE 7

TABLE 8

TABLE 9

TABLE 10

Claims (1)

N-phenyl-N'-benzoyl urea of the following general formula (I) is characterized by reacting the substituted phenyl isocyanate of the following general formula (II) with benzamide of the following general formula (III) in the presence of a diluent or a solvent. How to make

In the above structural formula R is halogenoalkyl having 1 to 4 carbon atoms, R ¹ is hydrogen or halogen, R ² is halogen, nitro, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms, X is an oxygen atom or a sulfur atom, n is 0,1,2,3,4 or 5.