KR810000472B1 - Process for preparing benzoylurea derivatives - Google Patents

Abstract

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Description

Method for preparing benzoyl urea derivative

The present invention relates to a process for preparing substituted benzoyl urea derivatives which are compounds of formula (I) which are useful as insecticides.

In the above structural formula

R is a halogen, alkyl or nitro group,

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

It is already known that certain benzoyl urea compounds, for example 1- (2,6-dichlorobenzoyl) -3- (4-chlorophenyl) -urea, have pesticidal action. (Germany Publication No. 2,123,236)

It was found that the compound of formula (I) has a strong insecticidal action.

It is preferred when R is fluorine, chlorine, bromine, iodine, nitro or straight or branched chain alkyl having 1-5 carbon atoms (especially 1-2) and n is 1,2 or 3.

The present invention relates to a method for preparing the substituted benzoyl urea which is the compound of formula (I).

(A) the 6-amino-2,2,4,4-tetrafluoro-benz-1,3-dioxin compound of the following structural formula (II) with 6-substituted benzoyl isocyanate of the following structural formula (III), If necessary, in the presence of a diluent, or

(B) Substituted benzamide, a compound of formula IV, with 6-isocyanate-2,2,4,4-tetrahydro-benz-1,3-dioxin of formula V, Prepared by reaction in the presence of diluent.

The substituted benzoyl ureas according to the invention have surprisingly similar structures and have substantially better pesticidal activity than 1- (2,6-dichlorobenzoyl) -3- (4-chlorophenyl) -urea, which exhibits the same action. have.

If for example 6-amino-2,2,4,4-tetrafluoro-benz-1,3-dioxin and 2-ethyl-benzoylisocyanate are used as starting materials in the preparation (A) or 6-isocyanate When -2,2,4,4-tetrafluorobenz-1,3-dioxin and 2-fluoro-benzamide are used as starting materials in the preparation method (b), the reaction process can be expressed as follows. have.

(end)

(I)

Benzoyl Isocyanate (III) used as starting material [J. Org. Chem. 30/12, pages 4306-4307 (1965) and benzamide (IV) are known compounds (Beilstein, Handbook of Orgamz Chemoztry, Vol. 9, pp. 336).

Examples of each are as follows: 2-methyl-, 2-ethyl-, 4-methyl-4-ethyl, 2-chloro, 2-fluoro-, 2-bromo-, 2-urido-, 2, 6-dichloro-, 2,6-difluoro-, 2,6-dibromo-, 2,6-diido-, 2,3,6-trichloro-, 2,3,6-tribromo And 2,3,6-triyodo-benzoyl isocyanate and -benzamide

6-amino-2,2,4,4-tetrafluoro-benz-1,3-dioxin (II) and 6-isocyanate-2,2,4,4-tetrafluoro-benz used as starting materials -1,3-dioxin (V) is also a known compound (see German Publication No. 1,643,382).

The process for the preparation of the substituted benzoylurea according to the invention is carried out in the presence of a suitable solvent or diluent. Virtually all inert organic solvents, especially optionally chlorinated aliphatic and aromatic hydrocarbons (e.g. benzene, xylene, toluene, chlorobenzene, benzine, methylene chloride, chloroform, carbon tetrachloride), ethers (e.g. diethyl ether, dibutyl ether. Oxane), ketones (eg acetone, methylethylketone, methylisopropylketone and methylisobutylketone) and nitriles (eg acetonitrile and propionitrile) can be used for this purpose.

The reaction temperature in each reaction step can vary within a substantial range. In general, this reaction is carried out at 0 ° -120 ° C, preferably at 50 ° -80 ° C.

This reaction is generally carried out at atmospheric pressure.

In carrying out this process, the starting material is used in most cases in equimolar amounts. When either of the reagents is used in excess, no product is advantageously produced. The reactants are in most cases added together with any of the solvents described above and are usually stirred for an hour to several hours at elevated temperature until the reaction is complete. After cooling the mixture, the precipitated product is filtered off, washed, dried and recrystallized if necessary.

These compounds are usually obtained in crystalline form and are characterized by their melting point.

The substituted benzylureas according to the invention are active against plant pests and veterinary drugs against parasites (external parasites) of animals, for example parasitic fly larvae.

For this reason, the compounds according to the invention can be used successfully to protect plants or as pesticides in the veterinary art.

Since the active compound according to the present invention does not damage plants and causes moderate toxicity to warm-blooded animals, it is suitable for combating pests of arthropods, particularly pests that are problematic in agriculture, forestry, stored products and sanitation. . The compounds of the invention are usually active against all or some of the sensitive and resistant species and growth stages. The pests mentioned above are:

Isopoda rivers such as Onnicus assellus, armadillidium vulgare and Porcellio scaber; Dipropoda river, such as, for example, Braniulus gutta l tus; The Chilopoda river, for example geophilus carpop hagus and Scutigera species; Symphyla river, for example Scutigerella immaculata, for example Lepisma sacch arina;

Collembola, for example Onychiurns armatus; Orthoptera, for example, the wingwheel (Blatta orientahz), the Periplaneta americana, the Leucophaea maderae, the wheel (Blattella germanica), the Aketa dometicus domesticus, gryllotalpa spp, Loausta migratoria migratorioides, melanoplus differentializ and Schistoc er ca gregaria; Permaptera, for example Porficula aurrcularia; Isoptera, for example Reticulitermes spp; Gnoplura, for example Phylloxera vastrix, Pemphigus spp, Pebiculus humanus corporis, Haematopinus subspecies, and Linognathus subspecies (Linograthus spp); Mallophaga, for example Trichodectes subspecies and Damalinea spp; Thysanoptera, for example Hercinothrips fomoralis and Thrips tabaci; Heteroptera, for example, Eurygaster spp, Dysdercus intermedius, Diesma quadrata, Cimex lectularius, Rodnius praxis ( Rhodnius prolixus) and Triatoma spp;

Homoptera, for example aleurodes brassicae, Bemisia tabaci, Triareurodes vaporariorum, Aphids gossypii, Brevico Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Peach aphid (Hgalopterus arundians) Aphids (Macrosiphum avenae), aphid subspecies (myzus spp), Rorodon humuli, millet rim aphids (plhopalosiphum padi), Empoasca spp, Eusceris virotus Nephotettix cincticeps, Lecanium Corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata Rugenz lugens, aonidiella aurantii, aspidiotus hederae, Pseudococcus spp., and Psylla spp .; Lepidoptera, for example, Peptinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Apple moth (Hyponomeuta padella), Chinese cabbage moth (Plutella maculipennis), tent moth (malacosoma neustria), patterned white moth (Euproctis Chrysorrhoea), Rymantria spp. , Phyllocnistis citrella, agrotis spp., Moth (Euxoa spp.), Feltia spp., Earias nsulana, Heliotis subspecies spp.), Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litara, Spodoptera spp. , tree Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp.Pyrarsta nubilalis, Efestia kuhniella Ephestia kuehniella, galleria mellonella, Cacoecia podana, Capua reticcu lana, Choristoneura fumiferana, Clysia ambigrella Homona magnanima and Tortrix viridana; Coleoptera, for example anobinum punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus , Hiltrupes bajulus, agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabirotica spp. .), Psylliodes chrysocephala, Epilapna varivestis, Atomaria spp., Oryzaephilus surinamensis, Antononomus spp. ), Sitophilus, Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhius gnchus assimilis, Hyperapostica, Dermestes spp., Trogoderma spp., Anthrenus spp., Athenus spp. ), Lgctus spp., Melligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides , Tribolium spp., Tenebrio molitor, Agriotes spp., Connderus spp., Melonta melolontha, Amphi Amphimallon solstitialis, and Costelytra zealandica; Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharmonis, and Vespi Subspecies (Vespa spp.);

Diptera spp., For example

des spp.), 아노페레스 아종(anopheles spp.), 쿠렉스 아종 (Culex spp.), 노랑초파리(Drosophila melanogaster), 집파리(Musca spp.), 아기집파기(Fannia spp.), 칼리포라 에리스로 세파라(Calliphora erythrocephala), 루시리아 아종(Lucilia spp.), 크리소마이아 아종(Chrysomgia spp.), 쿠테레브라 아종 (Cutereber spp.), 가스트로피루스 아종(gutrophilus spp.), 하이포보스카 아종 (Hyppobosca spp.), 스토목시스 아종(Stomoxys spp.), 오에스트루스 아종(Oestrus spp.), 히이포데르마 아종(Hypoderma spp.), 타바누스 아종(Tabanus spp.), 탄니아 아종(Tannia spp.), 비비오 호르투라누스(Bibio hortulanus), 오스시넬라 프리트 (Oscinella frit), 포르비아 아종(Phorbia spp.), 페고마이아 히오스시아미(Pegomyia hyoscyami), 세라티티스 카피티타(Cerattis Capitata), 다커스 오레아에(Dacus oleae) 및 티프라 파루포사(Tipula paluclosa.), 시포나프테라목(Siphonaptera), 예, 크세노르실라 케옵시스(Xenopsylla cheopis) 및 세라토필루스 아종(Ceratophyllus), 거미강(arachnicla), 예, 스콜피오 마우루스(Scorpio maurus) 및 라트로덱투스 막탄스(Latrodectus mactans).Aedes subspecies (a

des spp., anopheles spp., Curex spp., Drosophila melanogaster, Musca spp., Fannia spp., Califora erythro separa (Calliphora erythrocephala), Lucilia spp., Chrysomgia spp., Cutereber spp., Gustroilus spp., Hypoboska subspecies ( Hyppobosca spp.), Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tanania spp. ., Biobio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Cerattis Capitata. ), Dacus oleae and Tipula paluclosa., Siphonaptera, eg, Xenopsylla cheopis and Ceratophyllus, arachnicla, such as Scorpio maurus and Latrodectus mactans.

The active compounds are solutions, emulsions, hydrating agents, suspensions, powders, powders, blowing agents, pastes, water solubles, granules, aerosols, suspension-suspension concentrates, seed treatment powders, natural and synthetic substances with active substances. It can be prepared in the form of conventional formulations, such as very fine capsules made of polymerized materials and coated compositions, and used in seeds in the form of fume cartridges, fume cans, fume coils and in the lowest doses and cold and warm preparations.

Such formulations may be prepared using known methods, for example, active agents by weight, ie, liquid or solid or liquefied gaseous diluents or carriers, if necessary, with surfactants, ie emulsifiers and / or dispersants and / or blowing agents. Prepared by mixing. When water is used as the extender, an organic solvent may be used as the cosolvent.

Liquid diluents or carriers and especially solvents include xylene, toluene, benzene or alkyl-naphthalene, chlorinated aliphatic and aromatic hydrocarbons (e.g. chlorobenzene, chloroethylene, or methylene chloride), aliphatic or cycloaliphatic hydrocarbons (e.g. cyclohexane) or paraffins. (E.g. mineral oil fractions), alcohols (butanol or glycol) and ethers, ester ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone) or highly polar solvents (e.g. dimethylformamide , Dimethyl sulfoxide) and water.

Gaseous rare diluents or carriers which are liquids are liquids which may be gases at room temperature and atmospheric pressure, for example aerosol jetting agents such as dichlorodifluoromethane or trichlorofuluromethane.

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

Preferred examples of emulsifiers and blowing agents are anionic and cationic emulsifiers, including polyoxyethylene-fatty acid esters, polyoxyethylene fatty alcohols, ethers (eg alkylaryl polyglycol ethers), alkylsulfonates, alkylsulfates and arylsulfos Nate, albumin hydrolysis product. Preferred as dispersants are, for example, lignin sulfite waste liquors and methylcellulose.

Binders such as carboxymethylcellulose and powder, granular or crystalline nonsynthetic and synthetic polymers (eg, gum arabic, polyvinyl alcohol, polyvinylacetate) can be used in the formulation.

Inorganic pigments such as iron oxide, titanium oxide and Prussian blue, dyes of organic dyes such as azo dyes, azo dyes or coloring substances such as metal phthalocyanine dyes, and micronutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used. .

Such formulations generally contain from 0.1-95% (by weight) of active ingredient, preferably from 0.5-90% (by weight).

The active ingredient according to the present invention is used in the form of a commercially available formulation or in a form that can be used from such a formulation.

The active ingredient content in formulations which can be prepared and used in commercially available formulations can vary widely. The active ingredient concentration in the use form is 0.0000001-100% by weight, preferably 0.01-10% by weight.

The compound according to the present invention is used in a conventional manner using a specific use form.

When used against insects that are detrimental to health and pests present in stored products, the compounds of the present invention not only show good safety against calcareous alkalinity, but also show good residual activity in woody parts and clays.

In the field of veterinary use, the active substances according to the invention can be administered orally, immersed, sprayed, poured, applied or powdered in known methods, for example in the form of tablets, capsules, potions and granules. It is used parenterally, for example as an injection.

The present invention also provides a composition for insecticides in which a gaseous diluent or carrier which is a solid or a liquid, or a liquid diluent or carrier containing a surfactant is mixed with a compound of the present invention to contain the compound of the present invention as an active ingredient.

The present invention also provides a method for combating arthropods (particularly pests) by applying a composition form containing the compound of the present invention as an active ingredient alone or by mixing with a diluent or carrier to the arthropod or its habitat. Related.

The invention also relates to a method of protecting a livestock from ectoparasitic pests by applying the compound according to the invention to a livestock by mixing with a diluent or carrier.

The invention also applies to crops produced by arthropods by applying the compounds of the invention, either directly or before growing, or in combination with diluents or carriers, to areas where arthropods are growing. It also involves protecting from.

It will be appreciated that conventional methods of protecting harvested crops may be improved by the present invention.

The invention also relates to livestock capable of removing or protecting external parasitic insects by applying the compounds according to the invention in admixture with diluents or carriers to the aforementioned animals.

The pesticidal action of the compounds of the present invention are detailed by the following biological tests.

In the test examples, the active compounds according to the present invention are the same as the parentheses in the preparation examples described below.

[Test Example (A)]

Flutella Test

Solvent: Dimethylformamide 3 minutes (weight)

Emulsifying agent: alkylaryl polyglycol ethyl 1 minute (weight)

To prepare a suitable formulation of the active compound, 1 part (by weight) of the active compound is mixed with the aforementioned amount of solvent containing the aforementioned amount of emulsifier and the concentrate is diluted with water to the desired concentration.

The leaves of Cabbage (Brassica oleracea) are sprayed with an active compound until dew forms, and then infected with caterpillars of Platella maculipennis.

After a certain time, the degree of injury is expressed as a percentage. 100% of all caterpillars were killed, while 0% of no caterpillars were killed.

The active compounds, the concentrations of the active ingredients, and the evaluation time can be found in Table 1 below.

TABLE 1

Example 1

Parasitic Fly Larva Test

Solvent: Ethylene polyglycol monomethyl ether 35 minutes (weight)

Emulsifying agent: Nonylphenol polyglycol ether 35 minutes (weight)

To prepare a suitable formulation of the active compound, the concentrate obtained by mixing 30 minutes (by weight) of the active compound to be tested with the aforementioned amount of solvent containing the emulsifying agent described above is diluted with water to the desired concentration.

Twenty fly larvae (Lucilia cuprina resistant species) are placed in a test tube containing about 2 cm 3 of horse muscle. 0.5 ml of the active compound formulation is added to this horse. The percentage of injury is indicated after 24 hours. 100% of all larvae are killed and 0% of no larvae are killed.

The active compounds, the concentrations of the active compounds and their results can be found in Table 2 below.

TABLE 2

The manufacturing method which concerns on this invention is detailed by the following manufacture example.

[Production Example 1]

6.7 g (0.03) of 6-amino-2,2,4,4-tetrafluorobenz-1,3-dioxin at 60 ° C. in 20 ml of a toluene solution of 5.5 g (0.03 mol) of 2,6-difluorobenzoyl isocyanate at 60 ° C. Mole) is added dropwise to 100 ml of toluene solution. The batch was stirred for 1 hour at 60 ° C., cooled, and the precipitated product was filtered off, first washed with toluene, then petroleum ether and dried to give pure 3- (2,2,4,4-tetra). 8 g (65.5% of theory) of fluoro-benz-1,3-dioxin-6-yl-1- (2,6-difluorobenzoyl) -urea are obtained Melting point: 231 ° C.

The following compounds are prepared in the same manner as in Preparation Example 1.

Claims (1)

Reacting the next compound of formula (II) 6-amino-2,2,4,4-tetrafluoro-benz-1,3-dioxin with the following compound of formula (III) substituted benzoyl isocyanate or Substituted benzamide, a compound of formula IV, is reacted with 6-isocyanate-2,2,4,4-tetrafluoro-benz-1,3-dioxin, A process for preparing benzoylurea, which is a compound of formula (I).

In the above structural formula R is halogen, alkyl or nitro n is 1, 3, 2, 4 or 5.