DK157679B - N-BENZOYL-N'-PHENOXYPHENYLURINE INGREDIENTS, PESTICIDES AND PROCEDURES FOR COMBATING Harmful Organisms - Google Patents

Abstract

1. An N-benzoyl-N'-phenoxyphenylurea of the formula see diagramm : EP0057888,P13,F1 where Z is chlorine in the 3-position or methyl, R is fluorine, chlorine, bromine, phenoxy which is unsubstituted or substituted by fluorine, chlorine, bromine, or haloalkyl or haloalkoxy of up to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms which is unsubstituted or substituted by chlorine and/or fluorine, alkyl of 1 to 3 carbon atoms, or 2-hydroxy-hexahaloisopropyl, halogen being fluorine and/or chlorine, Y is hydrogen, fluorine or chlorine, X is fluorine, chlorine, bromine, methyl or nitro, the substituents X being identical or different, and n is 2 or 3, or where Z can also be hydrogen when R is phenoxy which is unsubstituted or substituted by fluorine, chlorine, bromine, or haloalkyle or haloalkoxy of up to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms which is unsubstituted or substituted by chlorine and/or fluorine, alkyle of 1 to 3 carbon atoms, or 2-hydroxyhexahaloisopropyl, halogen being fluorine and/or chlorine, Y is hydrogen, fluorine or chlorine, X is fluorine, chlorine, bromine, methyl or nitro, the substituents X being identical or different, and n is 1, 2 or 3, or where Z can also be hydrogen when R is fluorine or bromine, Y is chlorine, X is fluorine, chlorine, bromine, methyl or nitro, and n is 1, or where Y can also be bromine or nitro when R is fluorine, chlorine, bromine, phenoxy which is unsubstituted or substituted by fluorine, chlorine, bromine, or haloalkyl or haloalkoxy of up to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms which is unsubstituted or substituted by chlorine and/or fluorine, alkyl of 1 to 3 carbon atoms, or 2-hydroxy-hexahaloisopropyl, halogen being fluorine and/or chlorine, Z is hydrogen, chlorine in the m-position or methyl, X is fluorine, chlorine, bromine, methyl or nitro, the substituents X being identical or different, and n is 1, 2 or 3.

Description

DK 157679B

The invention relates to novel N-benzoyl-N'-phenoxy-phenylureas, pesticides for harmful organisms containing these compounds as active substances, and a method for controlling harmful organisms.

It is already known that N-benzoyl-N1-phenylureas can be used as insecticides (J. Agr. Food Chem. 21, 348 (1973); DE Publication No. 25 31 202).

However, the insecticidal activity of these known N-benzoyl-N1 -10 phenylureas is unsatisfactory.

It is thus the object of the invention to provide N-benzoyl-N'-phenylureas which exhibit better insecticidal activity than the known N-benzoyl-N'-phenylureas.

The N-benzoyl-N'-phenoxyphenylureas according to the invention are characterized in that according to the characterizing part of claim 1.

The invention further relates to a pesticide peculiar to the characterizing part of claim 4.

Finally, the invention relates to a method for controlling harmful organisms which is characterized by the method of claim 5.

It has been found that the compounds of the invention fulfill the object of the invention in that they can fight harmful organisms, especially insects, in a more effective way than known N-benzoyl-N'-phenoxyphenylureas. This will be documented by comparative experiments which figure 30 later in this specification and which include 2

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a large number of widely varying urea derivatives according to the invention with respect to the substituents R, Z, X and Y. During these comparison experiments, the following comparison compounds representing the prior art are used: A N- (2-methyl-benzoyl) -N - [3-Chloro-4- Example 3 from (4-chlorophenoxy) -phenyl] -urea DE-A-25 31 302 B N- (2-chloro-benzoyl) -N1- [3-chloro-4-Example 2 from (4-chlorophenoxy) phenyl] urea DE-A-25 31 202 10 C N- (2,6-dichlorobenzoyl) -N '- [4- Example 14 from (4-chlorophenoxy) phenyl] - urea Table III in J. Agr. Food, Chem. page 353

Examples of the meaning of R comprising a chloro and / or fluorine substituted alkoxy group having 1-4 carbon atoms may be cited: trifluoromethoxy, 1,1,2,2-15 tetrafluoroethoxy, difluoromethoxy, 2-chloro2,1,1 trifluoroethoxy and 1,1,2,3,3,3-hexafluoropropoxy, as examples of the meaning of R comprising an alkyl group of 1-3 carbon atoms, must be mentioned: methyl, ethyl, n-propyl and isopropyl, preferably methyl, and as examples of the meaning of R comprising a 2-hydroxyhexahalogen isopropyl group, the 2-hydroxyhexafluoro-isopropyl group, 2-hydroxychloropenta-fluoroisopropyl group, 2-hydroxy-dichlorotetrafluoroisopropyl group,

Preferred compounds of formula (I) are those in which X is chlorine at the o-position and n is 1 or X is chlorine or fluoro at the o-position and n is 2.

3

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The N-benzoyl-N'-phenoxyphenylureas of formula I are prepared by a) reacting a compound of formula

__ R

(Ii)

Y Z

wherein Y, Z and R have the meanings specified in claim 1, with a benzoyl isocyanate of the formula

Xn - wherein X and n have the meanings given in claim 1, or b) reacting a compound of the formula

R

QCN- ^ ~ ^ -0 - ^^ · (IV)

Y Z

wherein Y, Z and R have the meanings given in claim 1, with a benzamide of formula (V)

V

10 wherein X and n have the meanings specified in claim 1.

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Both reactions are preferably carried out in solvents or diluents. As such, virtually all inert organic solvents are considered. These include in particular aliphatic and aromatic, optionally chlorinated or nitrated hydrocarbons such as benzene, chlorobenzene, gasoline, carbon tetrachloride, 1,2-dichloroethane, methylene chloride, nitromethane, cyclic and acyclic ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxide. ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, and nitriles such as acetonitrile and benzonitrile. Mixtures of these solvents may also be used.

By reaction a) the reaction temperature can be varied within a larger range. It is usually between 0 and 80 ° C, preferably between 20 and 60 ° C. In this preferred range, the reaction proceeds without further cooling. In reaction b), the temperature can be varied between 20 and 160 ° C, and preferably at a temperature between 80 and 130 ° C.

Generally, the reaction is allowed to proceed under normal pressure.

The reaction components are preferably used in equimolar ratio. An excess of one or the other component 25 produces no significant advantages. The turnover is practically quantitative.

The compounds of the invention usually appear in the analyzer state; otherwise, they can be further purified by recrystallization. Elemental analysis and melting point serve to characterize it.

In implementing the method variant a) brings

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Suitably, the substituted aniline of formula II is co-existent with the solvent or diluent and then an equimolar amount of isocyanate of formula III is added. After a reaction time of 5 hours, usually two hours, the product is aspirated,

or the reaction solution is freed from solvent on a rotary evaporator. The product is then dried under reduced pressure. In process variant b) the reaction duration is 2 to 6 hours. The pehoxyanilines 10 of formula II and the benzoyl isocyanates of formula III

can be prepared according to known methods (J.

Org. Chem. 2J3, 1805 to 1811 (1963)); Weygand-Hilgetag, Organic-Chemical Experimental Art, 4th edition, J.A. Barth-Verlag, Leipzig, 1970, pp. 374, 510 (ff). The amine groups of the compounds of formula II can, according to known methods, e.g. by reaction with phosgene, is converted to the isocyanate group to give the compounds of formula IV.

Preparation Example 20 7.1 g of 3-bromo-4- (4-fluorophenoxy) aniline are dissolved at room temperature in 50 ml of toluene. Then 4.9 g of 2,6-difluorobenzoyl isocyanate is added dropwise, raising the temperature to 15 ° C. Then stir for an hour at 50 ° C, cool and suck the precipitate. 8.5 g of N- (2,6-difluoro-benzoyl) -N '- [4- (4-fluorophenoxy) -3-bromophenyl] urea are obtained, m.p. 162-164 ° C (active substance # 1).

The following connections are possible e.g. prepare by analogy to the above process a) or according to process b): ~ n y z 6

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No. Y Z R m.p. [° C] 2 2-F, 6-F Cl H 4-0CHF2 148-153 3 2-F, 6-F Cl H 4-0CD2CHClF 156-159 4 2-C1, 6-C1 Cl H 4-0CHF2 f 171-174 5 2-C1, 6-C1 Cl H 4-0CF2CHClF 129-139 6 2-C1 Cl H 4-0CF2CHClF 128-130 7 2-C1, 6-C1 Cl 3-C1 4-C1 240-242 8 2-C1 Cl 3-C1 4-C1 200-202 9 2-F, 6-F Cl 3-C1 4-C1 217-220 10 2-F Cl 3-C1 4-C1 186-187 11 2-F, 6-F Cl H 4-C (OH) (CC ^) 2170-185 12 2-C1 Cl H 4-C (OH) (CF3) 2165-177 13 2-C1 Η H 4-0CF2-CHClF2169-173 14 2-F, 6-F Η H 4-0CF2-CHClF2184-186 15 2-C1 Cl H 4-Br 155-156 16 2-C1 Br H 4-F 162-164 17 2-C1, 6-C1 FH 4 -CH ^ 212-217 18 2-C1 FH 4-CH3 168-173 19 2-F, 6-FDH 4-CH? 195-200 20 2-F, 6-F N02 H 4-C1 196-200 21 2-C1 N02 H 4-C1 186-191 22 2-F, 6-F HH 4-0CHF2 214-216 23 2-F , 6-F Cl H 4-0CF2CHFCF3 144-146 24 2-F, 6-FH 3-C1 5-C1 220-225 25 2-C1, 6-C1 H 3-C1 5-C1 231-234 26 2- C1 H 3-C1 5-C1 223-226 27 2-C1, 6-F Cl H 4-0CHF2 125-133 28 2-F, 6-F Cl H 4-0CF2CF2H 140-142 29 2-C1 Cl H 4 The 0CF2CF2H 136-138 N-benzoyl-N'-phenoxyphenylureas of formula I according to the invention are well suited to effectively control harmful organisms from the class of insects. They are suitable for adulticides and ovicides and 5 can be used for plant protection as well as for hygiene, 7

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the stock protection and veterinary sector as pesticides for harmful organisms.

Among the harmful insects, the order includes extensive butterflies (Lepidoptera), for example. Plutella maculi-5 pennis, Leucoptera coffeella, Hyponomeuta malinellus,

Argyresthia conjugella, Sitotroga cerealella, Phtho-rimaea operculella, Capua reticulana, Sparganothis pil-leriana, Cacoecia murinana, Tortrix viridana, Clysia ambiguella, Evetria buolina, Polychrosis botrana, Cydia 10 pomonella, Laspeyresia molesta,

Ostrinia nibilalis, Loxostege sticticalis, Ephestia kuehniella, Chilo suppressalis, Galleria Mellonella, Malacosoma neustria, Dendrolimus pini, Thaumatopoea pityocapa, Phalera bucephala, Chemimatobia brumata, 15 Hibernia defoliria, Bupalus

Agrotis ypsilon, Barathra brassica, Cirphis unipuncta, Prodenia litura, Laphygma exigu, Panolis flammea, Earias insulana, Plusia gamma, Albama argillacea, Lymantria dispar, Lymantria monocha, Pieris brassicae, Aporia 20 crataegi; from the order comprising beetles (Coleoptera) e.g. Bli-tophaga undata, Melanotus communis, Limonius californicus, Agriotes lineatus, Agriotes obscurus, Agrilus sinuatus, Meligthes aeneus, Atomaria linearis, Epilachna varives-25 tris, Phyllopertha horticola, Popillia japonica, Melolontha melolontha melolontha melolontha , Crioceris asparagi, Lema melanopus, Leptinotarsa decemlineata, Phaedon cochleariae, Phyllo-treta nemorum, Chaetocnema tibialis, Phylloides chry-, 30 socephala, Diabrotica 12-punctata, Cassida nebulosa,

Bruchus lentis, Bruchus rufimanus, Bruchus pisorum,

Sitona lineatus, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Hylobies abietis, Byctiscus betulae, Athonomus grandia, Ceuthorrhyncnus assimilis, Ceuthorrhynchus

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8 napi, Sitophilus granaria, Anisandrus dispar, Ips typographus, Blastophagus piniperda; from the order comprising the forceps (Diptera) e.g.

Lycoria pectoralis, Mayetiola destructor, Dasineura 5 brassicae, Contarinia tritici, Haplodiplosis equestris, Tipula paludosa, Tipula oleracea, Dacus cucurbitae,

Dacus oleae, Ceratitis capitata, Rhagoletis cerasi, Rhagoletis pomonella, Anastrepha ludens, Oscinella frit, Phorbia coarctata, Phorbia antiqua, Phorbia 10 brassicae, Pegomya hyoscyami, Anopheles maculipennis,

Culex pipiens, Aedes aegypti, Aedes vexans, Tabanus bovinus, Tipula paludose, Musca domestica, Fannia canicularis, Muscian stabulans, Glossina morsitans,

Oestrus ocis, Chrysomya macellaria, Chrysomya homini-vorax, Lucilia cuprina, Lucilia sericata, Hypoderma lineata; from the order comprising the veins (Hymenoptera) e.g. Athalia rosae, Hoplocampa minuta, Monomorium pharaonis, Solenopsis geminata, eight sexes; 20 from the order comprising wall lice (Heteroptera) e.g.

Nezara viridula, Eurygaster integriceps, Blissus leu-copterus, Dysdercus cingulatus, Dysdercus intermedium, Piesma quadrata, Lygus pratensis; from the order comprising plant cleaners (Homoptera) e.g.

25 Perkinsiella saccharicida, Nilaparvata lugens, Empoa-sca fabae, Psylla mali, Psylla piri, Trialeurodos vapo-r-iorum, Aphis fabae, Aphis pomi, Aphis sambuci, Aphidula nastrutii, Cerosipha gossypii, Sappaphis mala, Sappaphis mala Brachycaudus 30 cardui, Brevisoryne brassicae, Phorodon humili, Rhopa-lomyzus ascalonicus, Myzodes persicae, Hyzus cerasi, Dysaulacorthum pseudosolani, Acyrthosiphon onobrychis, 9

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Mscrosiphon rosae, Megoura viciae, Schizoneura lanuginosa, Pemphigus bursarius, Dreyfusia nordmannianae, Dreyfusia piceae, Adelges laricis, Viteus vitifolii; from the order comprising termites (Isoptera) e.g. Re-5 ticulitermes lucifugus, Calotermes flavicollis, Leuco- termes flavipes, Termes natalensis; and from the order comprising the retwingers (Orthoptera) e.g. Forficula auricularia, Acheta domestica, Gryllotalpa gryllotalpa, Tachycines, asynamorus, Locusta migratoria, 10 Stauronotus maroccanus, Schistocerca peregrina, Nomodacris septemfasciata, Melanopuls spretus, Melano plus femur-rubrum, Blatta orientalis, Blatta orientalis

The active substances can be used as such, in the form of their formulations or in accordance with the corresponding applications, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, powders, effluents, granules, 20 by spraying, mist formation, atomization, spattering or pouring. The applications are entirely based on the uses; they must in each case ensure the finest possible distribution of the active substances according to the invention.

For the preparation of direct-sprayable solutions, emulsions, pastes or oil dispersions, medium-high to high boiling mineral oil fractions such as petroleum or diesel oil, in addition coal oils and vegetable or animal origin oils, 30 aliphatic, cyclic and aromatic hydrocarbons, e.g.

benzene, toluene, xylene, paraffin, tetrahydroriaphthalene, alkylated naphtha, or their derivatives, e.g.

10

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methanol, ethanol, propanol, butanol, chloroform, tetrachlorocarbon, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, highly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 5 water, considered.

Aqueous applications can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by the addition of water.

For preparing emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by wetting, adhesive, dispersing or emulsifying agents. However, concentrates consisting of active substance, wetting agent, adhesive, dispersing or emulsifying agent and optionally solvent or oil may be prepared which concentrates are suitable for dilution with water.

As surfactants are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolic sulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutyl naphthalene sulfonic acid, laural sulfate 25 of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensates of sulfonated naphthalene and naphtalenderivater with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, 30 polyoxethylenoctylphenolether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl, alkylaryl polyether alcohols , isotridecyl alcohol, fatty alcohol ethylene oxide condenser, ethoxylated castor oil, polyoxyethylene alloy 11

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cooling ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolstheracetal, sorbitester, lignin, sulfite waste liquor and methyl cellulose under consideration.

Powder, scrubbing and powdering agents may be prepared by mixing or co-grinding the active substances with a solid carrier.

Examples of formulations are: I. 3 parts by weight of compound # 1 are thoroughly mixed with 97 parts by weight of finely divided kaolin. In this way, a powder containing 3% by weight of the active substance is obtained.

II. 20 parts by weight of compound # 14 are dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the preparation 13 product of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 5 parts by weight of the product of 40 moles of ethylene oxide. 1 mole of castor oil.

III. 80 parts by weight of Compound No. 17 are well mixed with 3 parts by weight of the sodium salt of diisobutyl-naphthalene alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor, and 7 parts by weight of powdered silicic acid rule and ground in a hammer mill.

Granules, e.g. envelope, impregnation and homogeneous granules can be prepared by bonding the active substances to solid carriers. Solid carriers are e.g. mineral soils, such as silica gel, silica, silica gels, silicates, talc, kaolin, aggregates, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium oxide, milled molds, fertilizers 12

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agents, such as e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and vegetable products, such as cereal, wood bark, wood and nut shell flour, cellulose powder and other solid carriers.

The formulations generally contain between 0.1 and 95% by weight of active substance, preferably between 0.5 and 90% by weight.

The concentration of active substance in the ready-to-use preparations can be varied within larger ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active substances can also be successfully used in the ultra-low volume method (ULV), enabling the application of formulations containing more than 95% by weight of 15% of active substance or even the active substance without additives.

The amount of active substance used under open-air conditions is between 0.02 and 10 kg / ha, preferably between 0.5 and 2.0 kg / ha.

20 To the active substances can be added oils of different types, herbicides, fungicides, other pesticides against harmful organisms, bactericides, possibly even just before use (tank mix). These agents may be provided to the agents of the invention in a weight ratio of 1:10 to 10: 1.

Eg. the following agents may be added: 1,2-dibromo-3-chloropropane, 1,3-dichloropropene, 1,3-dichloropropene + 1,2-dichloropropane, 1,2-dibromo-ethane, 2-sec-butylphenyl -N-methylcarbamate, o-chlorophenyl-N-methylcarbamate, 3-isopropyl-5-methylphenol-N-methylcarbamate

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13 bamate, o-isopropoxyphenyl-N-methylcarbamate, 3,5-dimethyl-4-methylmercapto-phenyl-N-methylcarbamate, 4-dimethylamino-3,5-xylyl-N-methylcarbamate, 2- (1, 3-dioxolan-2-yl) -phenyl-N-methyl-carbamate, 1-naphthyl-N-methylcarbamate, 2,3-dihydro-2,2-dimethyl-benzofuran-7-yl-N methyl carbamate, 2,2-dimethyl-1,3-benzodioxol-4-yl-N-methylcarbamate, 2-dimethylamino-5,6-dimethyl-4-pyrimidinyl-dimethylcarbamate, 2-methyl-2- (methylthio) -proplonaldehyde O- (methylcarbamoyl) oxime, S-methyl-N-10 [(methylcarbamoyl) -oxy] -thioacetimidate, methyl-N ', N'-dimethyl-N - [(methylcarbamoyl) oxy] -1-thiooxamidate, N- (2-methyl-chloro-phenyl) -N ', N'-dimethylformamidine, tetrachlorothiophene, 1 (2,6-difluoro-benzoyl) -3- (4-chloro-phenyl) -urea, 0.0 -dimethyl-O- (p-nitrophenyl) -phosphorothioate, 0,0-diethyl-O- (p-nitrophenyl) phosphorothioate, 0-ethyl-O- (p-nitrophenyl) -phenylphosphonothioate, 0, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate, 0,0-diethyl-O- (2,4-dichlorophenyl) phosphorothioate, O-ethyl-O- (2,4-dichlorophenyl) - phenyl-p hosphonothioate, 0.0-dimethyl-O- (2,4,5-trichlorophenyl) ethyl phosphonothioate, 0.0-dimethyl-O- (4-bromo-2,5-dichlorophenyl) phosphorothioate, 0 O-dimethyl-O- (2,5-dichloro-4-iodophenyl) phosphorothioate, 0,0-dimethyl-O- (3-methyl-4-methyl-thiophenyl) phosphorothioate, O-ethyl-O - (3-methyl-4-methylthiophenyl) -isopropyl phosphoramidate, 0,0-diethyl-O- [p-methylsulfinyl-phenyl] -phorphthioate, 0-ethyl-5-phenyl-ethyl-phosphonodithioate, O-diethyl- [2-chloro-1- (2,4-dichlorophenyl) -vinyl] -phosphate, 0,0-dimethyl - [- 2-chloro-1- (2,4,5-trichlorophenyl)] -vinyl phosphate, 0.0-dimethyl-5-C1'-phenyl) -ethyl acetate-phosphorodithioate, bis- (dimethylamino) -fluorophosphine oxide, octamethyl-pyro-phosphoramide, 0.0-0.0-tetraethyl-dithio-pyrophosphate, S-chloromethyl-0,0-diethyl phosphorodithioate, 0-ethyl-S, S-dipropyl phosphorodithioate, 0,0-dimethyl-2,2-dichlorovinyl-phosphate, 0,0-dimethyl-1,2 -dibromo2,2-dichloro-ethyl phosphate, 0,0-dimethyl-2,2,2-trichloro-1-hydroxy-14

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ethyl phosphonate, 0.0-dimethyl-S- [1,2-biscarbethoxyethyl (1)] phosphorus dithioate, 0-O-dimethyl-O- (1-methyl-2-carb-methoxy-vinyl) phosphate, 0.0 -dimethyl-5- (N-methyl-carbamoyl-methyl) phosphorus dithioate, 0,0-dimethyl-S- (N-5-methylcarbamoyl-methyl) -phosphorothioate, 0,0-dimethyl-S- (N-methoxyethyl) -carbamoylmethyl) phosphorus dithioate, 0,0-dimethyl-S- (N-formyl-N-methyl-carbamoylmethyl) phosphorus dithioate, O, Q-dimethyl-O- [1-methyl-2- (methyl carbamoyl) vinyl] phosphate, 0,0-dimethyl-O - [(1-methyl-2-10 dimethylcarbamoyl) vinyl] phosphate, 0,0-dimethyl-0 - [(1-methyl-2 chloro-2-diethylcarbamoyl) -vinyl] -phosphate, 0.0-diethyl-S- (ethylthio-methyl) phosphorodithioate, 0,0-diethyl-S - [(p-chloro-phenylthio) -methyl] -phosphorodithioate, 0.0-dimethyl-S- (2-ethylthioethyl) phosphorothioate, 0.0-15 dimethyl-S- (2-ethylthioethyl) phosphorodithioate, 0.0-dimethyl-S- (2-ethylsulfinyl-ethyl) phosphorothioate, 0.0-diethyl-S- (2-ethylthio-ethyl) phosphorus dithioate, 0.0-diethyl-S- (2-ethylsulfinyl-ethyl) phosphorothioate, 0.0-diethyl-thiophosphorus yliminophenyl-acetonitrile, 0.0-20 diethyl S- (2-chloro-1-phthalimidoethyl) phosphorus dithioate, 0,0-diethyl-S- [6-chloro-benzoxazolone- (2) -yl- ( 3)] - methyl-dithiophosphate, 0,0-dimethyl-S- [2-methoxy-1,3,4-thia-diazole-5- [4H] -onyl- (4) -methyl] -phosphorodithioate, O-diethyl-O- [3,5, é-trichloropyridyl- (2)] phosphorothioate, 0,0-diethyl-O- (2-pyrazinyl) phosphorothioate, 0,0-diethyl-O- [2- isopropyl-4-methyl-pyrimidinyl (6)] phosphorothioate, 0,0-diethyl-O- [2- (diethylamino) -6-methyl-4-pyrimidinyl] -thionophosphate, 0.0-dimethyl-S - (4-oxo-1,2,3-benzotriazine-3- [4H] -ylmethyl) phosphorus dithioate, 0.0-dimethyl-S - [(4,6-diamino-1, 3,5-triazin-2-yl) methyl] phosphorus dithioate, 0,0-diethyl- (1-phenyl-1,2,4-triazol-3-yl) -thione phosphate, O, S-dimethyl phosphorus amido-thioate, 0, 5-dimethyl-N-acetyl-phosphorus-amidothioate-hexachlorocyclohexane, 1,1-di (p-methoxyphenyl) -2,2,2-trichloroethane, 6,7,8, 9,10,10-hexachloro-1,5,5a, 6,9,9a-hexahydro-6,9-15

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methano-2,4-3-benzodioxa-thiepen-3-oxide, pyrethrins, DL-2-allyl-3-methyl-cyclopenten- (2) -one- (1) -yl- (4) -DL-cis, trans-chrysanthemate, 5-benzyl-furyl- (3) -methyl-DL-cis, trans-chrysanthemate, 3-phenoxybenzyl (+) - cis, trans-2,2-dimethyl-3- (2,2-dichlorovinyl) ) -cyclopropane carboxylate, α-cyano-3-phenoxybenzyl (+) - cis, trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane carboxylate, (s) -α-cyano-3-phenoxybenzyl-cis (1R, 3R) -2,2-Dimethyl-3- (2,2-dibromo-vinyl) -cyclopropane carboxylate, 3,4,5,6-tetrahydrophthalimidoethyl-DL-cis, trans-chrysanthemate, 2-methyl -5- (2-propinyl) -3-furylmethyl-chrysanthemate and (α-cyano-3-phenoxybenzyl) -α-isopropyl-4-chlorophenyl acetate.

The following examples document the biological effect of the new compounds.

15 The numbering of the active substances corresponds to the table.

Example 1

Breeding experiments with mosquito larvae (Aedes aegypti).

200 ml of tap water are mixed with active 20 compositions containing 10% by weight of active substance and 90% by weight of an emulsifier mixture of 10% by weight ethoxylated castor oil, 20% by weight ethoylated isooctylphenyl and 70% by weight cyclohexanone, and then 30 to 40 Aedes larvae are applied at 4 'stage.

The test temperature is 25 ° C. The puncture and adult individuals are judged from the pupal sheath, which is used as a measure of untreated control. For the duration of the experiment of 10 to 12 days, a regular, powdery 30 fish feed is fed once.

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16

In this experiment, active substances Nos. 1, 2, 3, 4, 6, 9, 11, 12, 14, 15, 16, 18, 19, 20, 22, 24, 26 and 27 show a better effect than the comparators.

This is shown in the following table.

Active substance Concentration of Mortality Rate No. of Active Substance [ppm] [%] 1 0.05 100 2 0.01 100 3 0.1 100 4 0.02 100 6 0.1 100 9 0.04 100 11 0.02 100 12 0.08 100 14 0.02 100 15 0.05 100 16 0.1 100 18 0.5 100 19 0.2 100 20 0.2 100 22 0.02 100 24 0.004 100 26 0.4 100 27 0.1 100 A 1.0 100 A 0.5 4.50 B 0.1 100 B 0.04 <180 5 Example 2

Breeding experiments with house flies (Musca domestica) 50 g of a substrate of 100 parts of water 17

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10 parts of baking yeast 10 parts of dry milk 1 part of agar is thoroughly mixed in hot state with the aqueous composition of a mixture of 10% by weight of the active substance and 90% by weight of a mixture of wetting agent and inert carrier.

After cooling, the substrate is coated with approx. 0.1 ml of fly eggs and observe its development over a week.

The test temperature is at 20 ° C.

During this experiment, active substances Nos. 11, 14, 22 and 27 show an excellent effect, while the comparative agents are inactive. This is shown in the following table.

Active substance Concentration of the Effect No._active substance [ppm] _ [? □] _ s 11 25.0 Total inhibition 14 2.5 Total inhibition 22 5.0 Total inhibition 27 2.0 Total inhibition A 25.0 Inactive C 50.0 Inactive

Example 3 Growth test with Mediterranean fruit flies (Ceratitis capitata).

The tests are carried out in 100 ml plastic cups filled with 40 g of a substrate of carrot powder and water (1: 3) with yeast addition. The active substance is introduced as 20 aqueous preparation into the finished porridge and inoculated with 100 to 200 fresh eggs. The cups are stored in a closed state at 24 to 26 ° C; after approx. one week course 18

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one can judge the development.

In this experiment, active substances Nos. 2, 4 and 22 show a stronger effect than comparator A.

Example 4 5 Growing experiments with rice flour beetles (Tribolium castaneum) 10 grams of wheat flour thoroughly mixed with 0.02 or 0.5 mg of active substance are loaded into 250 ml plastic bottles and coated with 20 rice flour bees. After the egg laying (after 14 days) you aim the beetles. The flour is filled back into the bottles and stored until the teat casing of the next beetle generation at + 24 ° C.

In this experiment, active substances # 2, 4 and 6 show a better effect than comparator A.

Example 5 15 Sealing test with cotton-walled lice (Dysdercus intermedius) 50 g of cotton seed seed are introduced for swelling for 24 hours in the aqueous composition of 10% by weight active substance and 90% by weight of an emulsifier mixture. of 10 wt% ethoxylated castor oil, 20 wt% ethoxylated isooctylphenol and 70 wt% cyclohexanone.

The above liquid is poured.

Then 20 wall lice are introduced into the penultimate larval stage in 1 liter glass, the bottom of which is covered with moist 25 sand. These animals get the pre-treated seeds for only 7 days as the only food. Then they offer them untreated feed.

19

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It is observed whether the animals a) survive and b) change skin to become adult individuals.

During this experiment, the active substance # 38 shows a better effect than the comparators. This is shown in the following table.

Active substance Concentration of Mortality Rate No. active substance (ppm) (%) 22 1 100 A 25 100 A 1 Inactive B 10 100 B 4 Inactive C 25 Inactive

Example 6

Breeding experiments with larvae of flour moth (Ephestia kueh-niella) 10 Wheat flour, which was largely coated with flour of eggs of flour, is thoroughly mixed with the active substances. 10 g of this flour is then filled into 250 ml glass bottles and stored at 22 ° C. After 4 weeks, the larval development is assessed.

In this experiment, active substances Nos. 2, 4, 6 and 22 show a strong effect.

Claims (5)

N-benzoyl-N'-phenoxyphenylureas, characterized in that they have the general formula B - / - G0-NH-CO-NH - / ^ - O - ^^ (I), η YZ wherein 5. is chlorine in 3-position, R is fluorine, chlorine, bromine, a chloro and / or fluorine-substituted alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms or a 2-hydroxyhexahalogenisopropyl group wherein halogen is 10 fluorine and / or chlorine, Y is hydrogen, fluorine, chlorine or bromine, X is fluorine, chlorine or bromine, and n is 2 or 3, whereby the substituents X are the same or different, wherein Z is also hydrogen when R is one with chlorine and / or fluoro substituted alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms or a 2-hydroxyhexahalogenisopropyl group, wherein halogen is fluorine and / or chlorine, Y is hydrogen, fluorine or chlorine, X is fluorine, chlorine or bromine. and n is 1, 2 or 3, whereby the substituents X are the same or different, wherein Z is also hydrogen when DK 157679B R is fluorine. or bromine, V is chlorine X is fluorine, chlorine or bromine, and n is 1, 5 wherein Y is also bromine or nitro when R is fluorine, chlorine, bromine, a chloro and / or fluorine substituted alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms or a 2-hydroxyhexahalogenisopropyl group wherein halogen is fluorine and / or chlorine, Z is hydrogen or chlorine at m-position X is fluorine, chlorine or bromine, and n is 1, 2 or 3, wherein the substituents X are the same or different. N-benzoyl-N'-phenoxyphenylureas of formula I according to claim 1, characterized in that Z is hydrogen, X is chloro in the o-position and n is 1. N-benzoyl-N'-phenoxyphenylureas of formula 20 I according to claim 1, characterized in that X is fluorine or chlorine in the o-position and that n is 2. A pest control agent, characterized in that it contains a solid or liquid carrier and an N-benzoyl-N'-phenoxyphenylurea of formula 25. according to claims 1-3. A method for controlling harmful organisms, characterized in that an active amount of an N-benzoyl-N'-phenoxyphenylurea of formula I according to claims 1-3 affects the harmful organisms or their whereabouts.