IE913652A1 - Diphenyl ethers - Google Patents

Abstract

Novel 3,5-diisopropyldiphenyl ether derivatives of the formula I in which X is fluorine or chlorine and Z is the bridge -NH-CS-NH- or -N=C=N- can be used as pesticides, preferably for controlling insects and spider mites.

Description

Diphenyl ethers The present invention relates to novel derivatives of 3,5-diisopropyldiphenyl ethers, to their preparation, to pesticidal compositions which contain these compounds and to the use thereof for controlling pests of the phylum of Arthropoda, preferably insects and representatives of the order Acarina.

The 3,5-diisopropyldiphenyl ether derivatives of this invention have the formula I CHfCH,)-, X CH(CH3)2 (I) wherein X is fluoro or chloro and Z is the bridge -NH-CS-NH- or -N=C=N-.

Insecticidally active phenylthioureas and phenylcarbodiimides of diphenyl ether structure are disclosed in the literature, for example in DE-OS 3034905 and EP-A-175649. However, the biological properties of the compounds disclosed in these publications are not entirely satisfactory in pest control. There is therefore a need to provide active compounds of this class having improved properties for controlling insects and representatives of the order Acarina. Surprisingly, it has been found that this requirement is substantially met by the compounds of this invention.

The group of compounds of formula I is subdivided into that of the 2,6-diisopropyl-4phenoxyphenylthioureas of formula Ia -2/ Vo_y > CH(CH3)2 NH-CS-NH-C(CH3)3 (Ia) CH(CH3)2 and that of the 2,6-diisopropyl-4-phenoxyphenylcarbodiimides of formula lb U-n ' \ N=C=N-C(CH3)3 CH(CH3)2 (lb) X CH(CH3)2 wherein X is fluoro or chloro.

Preferred compounds of each of formulae Ia and lb are those wherein X is chloro, namely N-2,6-diisopropyl-4-(2-chlorophenoxy)phenyl-N'-tert-butylthiourea and N-2,6-diisopropyl-4-(2-chlorophenoxy)phenyl-N'-tert-butylcarbodiimide.

The compounds of formula I may be prepared by methods analogous to known ones. For example, the compound of formula I is obtained by a) reacting an isothiocyanate of formula II / X X (Π) wherein X is as defined for formula I, with tert-butylamine of formula ΙΠ H2N-C(CH3)3 (ΠΙ) to give the thiourea of formula Ia X CH(CH3)2 and, if desired, b) converting the thiourea of formula Ia into the carbodiimide of formula Ib CH(CH3)2 N=C=N-C(CH3)3 (Ib) X CH(CH3)2 by removal of hydrogen sulfide.

Process a) is usually carried out under normal pressure and in the presence of an organic solvent or diluent. The reaction temperature is in the range from 0 to +150°C, preferably from +10 to +70°C. Typical examples of suitable solvents or diluents are: ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; Ν,Ν-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons such as benzene, toluene, xylenes, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; nitriles such as acetonitrile or propionitrile; and ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone and cyclohexanone.

Process b) is conveniently carried out in conventional manner in an aprotic organic solvent or diluent and under slightly elevated or normal pressure. The reaction temperature is in the range from 0 to +150°C, preferably from +10 to +50°C. Typical examples of suitable solvents or diluents are: ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; Ν,Ν-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons such as benzene, toluene, xylenes, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; .4. nitriles such as acetonitrile or propionitrile; and ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone and cyclohexanone. The removal of hydrogen sulfide is effected by methods described in the literature (Chemistry Letters 1977, p. 575-76; Tetrahedron Letters 1985, p. 1661-64; Ber. Dtsch. Chem. Ges. 6, 1873, p. 1398; Bull. Soc. Chim. 1956, p. 1360). Suitable reagents include HgO, specific pyridinium salts, chloroacetates, cyanuric chloride, p-toluenesulfonyl chloride or specific phosphoric acid ester derivatives.

In addition to the method outlined above, process b) can also be carried out by photochemical means (EP-A-307361), by oxidising the thiourea of formula Ia photochemically with oxygen to give the carbodiimide of formula Ib.

The photooxidation can be carried out with light of preferably 200 to 700 nm wavelength. When using UV light, for example in the UV-B range, the concurrent use of sensitisers can be dispensed with. It has been found convenient to carry out the photooxidation with UV light or visible light in the presence of a sensitiser. Suitable light sources are sunlight, halogen lamps, filament lamps for external exposure, sodium vapour lamps or mercury vapour lamps (as source of UV light). Suitable sensitisers foir producing singlet oxygen are typically: xanthene dyes, (Rose Bengal), thiazines (Methylene Blue), porphyrins (tetraphenylprophyrin), thionine, eosin, erythrosin, phenosafranin, chlorophyll, flavines, thioxanthones, phthalocyanines, thiophenes, naphthalene derivatives, phenothiazines, pyrazoleanthrones, ketocoumarins, azines (riboflavin), anthraquinones, metallocenes, benzophenones, anthracene derivatives. A preferred group of sensitisers comprises Methylene Blue, Bengal pink, tetraphenylporphyrin and phthalocyanines. The reaction can be carried out in the temperature range from typically -20°C to 50°C, preferably at room temperature (c. 15-35°C). Suitable solvents are inert organic organic solvents and mixtures of solvents and mixtures thereof with water. Exemplary of suitable solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons (pentane, hexane, cyclohexane, benzene, toluene), chlorinated hydrocarbons (methylene chloride, carbon tetrachloride, tri- or tetrachloroethane, chlorobenzene, alcohols (methanol, ethanol, ethylene glycol monomethyl ether), ethers (diethyl ether, dibutyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane), ketones (methyl isobutyl ketone), esters (ethyl acetate), nitriles (acetonitrile), Ν,Ν-disubstituted carboxamides and lactams (dimethyl acetamide, N-methylpyrrolidone), sulfones (tetramethylenesulfone). A preferred solvent is a mixture of acetonitrile and water. Sulfuric acid forms during the reaction. For this reason, it is convenient to use at least 2 equivalents, for example to 2.5 equivalents, of an acid -5acceptor. The acid acceptor may be typically an alkali metal or alkaline earth metal base, an alkali metal or alkaline earth metal carbonate or hydrogencarbonate or a buffer solution of pH > 7. Typical examples of such bases are LiOH, KOH, NaOH, Ca(OH)2, NaHCO3, CaHCO3, KHCO3. Suitable buffer mixtures of pH > 7 include aqueous solutions of borax/NaCl or KH2PO4, K3PO4, borax, NaHCO3, Na2HPO4 or KC1 and NaOH. It is preferred to use NaOH. The process can be carried out by introducing gaseous oxygen, such as pure oxygen, air or a mixture of oxygen and an inert gas into the reaction mixture. Exemplary of inert gases are nitrogen, carbon dioxide and rare gases such as helium, neon and argon. It is preferred to use singlet oxygen, especially if sensitisers are concurrently used. The photochemical process b) can be carried out by charging the compound of formula Ia, the acid acceptor, the solvent and the optional sensitiser to the reactor and stirring the mixture well in the presence of air while exposing it to light in an open system, or by passing oxygen or a mixture of oxygen and inert gas through the reaction mixture, with stirring, and exposing the reaction mixture to light. Working up is effected in conventional manner by extraction, washing and drying the extract and removing the solvent by distillation.

The isothiocyanates of formula II may be prepared by methods which are known per se by thiophosgenating an aniline of formula IV X (IV) wherein X is as defined for formula I.

The process for the preparation of the compounds of formula II is conveniently carried out in the presence of an organic or inorganic base such as triethylamine or calcium carbonate and in an inert solvent or diluent under normal pressure. The reaction is carried out in the temperature range from 0° to +100°C, preferably at the boiling temperature of the solvent or diluent employed, or in the range from +20°C to +80°C. Suitable solvents and diluents are typically ethers or ethereal compounds such as diethyl ether, diisopropyl ether, dioxane or tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene or xylenes; -6ketones such as acetone, methyl ethyl ketone or cyclohexanone; or chlorinated hydrocarbons such as dichloromethane. The reaction can also be carried out in the presence of water in a two-phase system.

The phenoxyanilines of formula IV can be prepared by methods which are known per se, for example by reacting an aniline of formula V (V) with a phenol of formula VI // \ OH (VI) X wherein X is as defined for formula I and Hal is halogen, preferably chloro and bromo.

The process for the preparation of compounds of formula TV is conveniently carried out in the presence of an organic or, preferably, inorganic base, for example an alkali metal hydroxide or alkali metal carbonate, and in an inert, preferably polar, solvent or diluent and under normal pressure. The process is carried out in the temperature range from 0° to 200°C, preferably at the boiling point of the solvent or diluent employed, or in the range from 50° to 170°C. It can be advantageous to add a heavy metal catalyst, for example copper powder or basic copper(II) carbonate. Examples of suitable solvents and diluents are amides such as dimethyl formamide, dimethyl sulfoxide, N-methylpyrrolidone and other aprotic dipolar solvents.

The compounds of formulae II and IV are novel and also constitute an object of the present invention. The compounds of formulae III, V and VI on the other hand are known and some are commercially available or can be prepared by methods which are known per se. -7It has now been found that the compounds of formula I of this invention are useful compounds in pest control and are well tolerated by warm-blooded animals, fish and plants. The compounds of this invention are applied especially against insects and arachnids which are pests in crop plants and ornamentals in agriculture, especially in cotton, vegetable and fruit crops, in forestry, in the storage and protection sectors and in the hygiene sector, especially pests of domestic animals and productive livestock. The compounds of formula I are effective against all or individual development stages of normal sensitive and also resistant species. Their activity may be observed in an immediate kill of the pests or not until after a time lapse, for example in moulting, or in diminished oviposition and/or hatching rate. The above mentioned pests include: of the order of the Lepidoptera, for example Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni und Yponomeuta spp.; of the order of the Coleoptera, for example Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp. Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. und Trogoderma spp.; of the order of the Orthoptera, for example Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; of the order of the Isoptera, for example Reticulitermes spp.; of the order of the Psocoptera, for example Liposcelis spp.; of the order of the Anoplura, for example Haematopinus spp., Linognathus spp. Pediculus spp., Pemphigus spp. and Phylloxera spp.; of the order of the Mallophaga, for example Damalinea spp. and -8Trichodectes spp.; of the order of the Thysanoptera, for example Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii; of the order of the Heteroptera, for example Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp. Eurygaster spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.; of the order of the Homoptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium comi, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; of the order of the Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; of the order of the Diptera, for example Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp. Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; of the order of the Siphonaptera, for example Ceratophyllus spp., Xenopsylla cheopis; of the order of the Acarina, for example Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; and of the order of the Thysanura, for example Lepisma saccharina.

The compounds are especially suitable for controlling pests in crops of cotton, fruit, citrus fruit and vegetables. The pests controlled are in particular spider mites such as Tetranychus urticae, Panonychus ulmi, Panonychus citri, Phyllocoptruta oleivora, Tetranychus cinnabarinus, larvae of chewing insects such as those of Plutella xylostella, and sucking -9insects such as Bemisia tabaci.

The good pesticidal activity of the compounds of formula I corresponds to at least 50-60 % kill of the above pests.

The activity of the compounds of this invention and of the compositions containing them can be substantially broadened and adapted to prevailing circumstances by addition of other insecticides and/or acaricides. Examples of suitable additives include: organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.

The compounds of formula I are used in unmodified form, or preferably together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the compositions, the methods of application such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compounds of formula are also suitable for use in the treatment of seeds. The seeds may be treated or dressed with the active compound or with a formulation containing it, or the active compound may also be applied to the furrow when sowing.

The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I or combinations thereof with other insecticides or acaricides, and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, in some cases, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide or water, vegetable oils such as rapeseed oil, -10castor oil, coconut oil or soybean oil; or also silicone oils.

The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. To improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the compound of formula I to be formulated, or of combinations thereof with other insecticides or acaricides, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term surfactants will also be understood as comprising mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22). e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, e.g. from coconut oil or tall oil. Further suitable surfactants are also the fatty acid methyltaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a C8-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate, or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical - 11 containing about 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corresponding phosphates, e.g. salts of the phosphated polyadduct of 4 mol of p-nonylphenol with 14 mol of ethylene oxide, or phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cg-C^alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyl bis(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described e.g. in the following publications: Me Cutcheon’s Detergents and Emulsifiers Annual, Me Publishing Corp., Glen Rock NJ USA, 1988, H. Stache, Tensid-Taschenbuch (Surfactants Manual), 2nd. ed., C. Hanser Verlag - 12M. and J. Ash. Encyclopedia of Surfactants, Vol. Ι-ΙΠ, Chemical Publishing Co., New York, 1980-1981.

Munich/Vienna 1981, The pesticidal compositions usually contain 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I or combination thereof with other insecticides or acaricides, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 20 %, of a surfactant.

Whereas commercial products are preferably formulated as concentrates, the end user will normally employ diluted formulations of substantially lower concentration. Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm. The rates of application per hectare are in general from 10 to 1000 g per hectare, preferably from 25 to 250 g/ha.

Preferred formulations are composed in particular of the following constituents (% = percentage by weight): Emulsifiable concentrates pesticide: surfactant: liquid carrier: to 50 %, preferably 5 to 30 % 5 to 30 %, preferably 10 to 20 % 20 to 94 %, preferably 50 to 85 % Dusts pesticide: solid carrier: 0.1 to 10 %, preferably 0.1 to 1 % 99.9 to 90 %, preferably 99.9 to 99 % Suspension concentrates pesticide: water: surfactant: Wettable powders pesticide: surfactant: solid carrier: to 75 %, preferably 10 to 50 % 94 to 25 %, preferably 90 to 30 % to 40 %, preferably 2 to 30 % 0.5 to 90 %, preferably 1 to 80 % 0.5 to 20 %, preferably 1 to 15 % to 95 %, preferably 15 to 90 % - 13Granulates pesticide: solid carrier: 0.5 to 30 %, preferably 3 to 15 % 99.5 to 70 %, preferably 97 to 85 %.

The compositions can also contain further ingredients such as stabilisers, typically vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams such as silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilisers or other chemical agents to obtain special effects.

The invention is illustrated by the following non-limitative Examples.

Working Examples Example W1: N-2,6-Diisopropyl-4-(2-chlorophenoxv)phenvl-N'-tert-butylthiourea NH-CS-NH-C4H9-t 8.5 g of 2,6-diisopropyl-4-(2-chlorophenoxy)phenylisothiocyanate are diluted with 50 ml of tetrahydrofuran and then 3.6 g of tert-butylamine are added at room temperature. The mixture is allowed to stand for 24 hours at room temperature and then heated for 6 hours to +40°C. The reaction mixture is poured into ice-water and the precipitate is isolated by filtration, washed with water and dried. Recrystallisation from hexane gives colourless crystals of pure N-2,6-diisopropyl-4-(2-chlorophenoxy)phenyl-N'-tert-butylthiourea of m.p. 151-152°C. ΙΕ 913652 - 14Example W2: N-2,6-Diisopropyl-4-(2-fluorophenoxy)phenyl-Nl-tert-butylthiourea C3H7-1 NH-CS-NH-C4H9-t E C3H7-1 In accordance with the general procedure of Example Wl, pure N-2,6-diisopropyl-4-(2fluorophenoxy)phenyl-N'-tert-butylthiourea of m.p. 150-152°C is obtained from 2,6-diisopropyl-4-(2-fluorophenoxy)phenylisothiocyanate and tert-butylamine.

Example W3: N-2,6-Diisopropyl-4-(2-chlorophenoxv)-phenyl-N'-tert-butylcarbodiimide 4.0 g of N-2,6-diisopropyl-4-(2-chlorophenoxy)phenyl-N'-tert-butyithiourea and 2.9 g of 2-chloro-l -methylpyridinium iodide are added to 30 ml of dry acetonitrile. Then 2.3 g of triethylamine in 20 ml of acetonitrile are added dropwise at room temperature and the mixture is stirred for 30 minutes at boiling temperature. The solvent is then removed under vacuum and the residue is taken up in hexane and the solution is filtered. The filtrate is washed three times with water, dried over sodium sulfate, decolourised with silica gel and freed from solvent under vacuum, giving pure N-2,6-diisopropyl-4-(2-chlorophenoxy)phenyl-N'-tert-butylcarbodiimide in the form of a colourless oil, nD20 = 1.5630.

Example W4: N-2,6-Diisopropyl-4-(2-fluorophenoxv)phenvl-N'-tert-butvlcarbodiimide C3H7-1 N=C=N-C4H9-t F C3H7-1 - 15In accordance with the general procedure of Example W3, pure N'-2,6-diisopropyl-4-(2fluorophenoxy)phenyl-N'-tert-butylcarbodiimide is obtained in the form of a colourless oil, ηθ23 = 1.5478, from 2,6-diisopropyl-4-(2-fluorophenoxy)phenyl-N'-tert-butylthiourea.

Example W5: 2,6-Diisopropyl-4-(2-chlorophenoxy)aniline Cl 67.2 g of 2-chlorophenol and 7.2 g of potassium carbonate are added to 200 ml of toluene. At room temperature, 58.7 g of a 50 % solution of potassium hydroxide is added dropwise over 50 minutes. The water formed is removed as an azeotrope at a bath temperature of 180°C and, after cooling, 5.9 g of copper carbonate and 350 ml of dimethyl formamide are added. The toluene is distilled off until the temperature of the mixture has reached 140°C. At this temperature, 67 g of 4-bromo-2,6-diisopropylaniline are added dropwise and the reaction solution is stirred for 20 hours. The reaction mass is subsequently completely concentrated by evaporation to remove the solvent. The residue is stirred in diethyl ether and filtered over diatomaceous earth. The filtrate is washed twice with 10 % aqueous sodium hydroxide and then with water and dried over sodium sulfate. The solution is concentrated by evaporation and the residue is chromatographed over silica gel (eluant: toluene), giving 2,6-diisopropyl-4-(2-chlorophenoxy)aniline as a colourless oil, nD21 = 1.5780.

Example W6: 2,6-Diisopropyl-4-(2-fluorophenoxy)aniline θαΙΆ-ί In accordance with the general procedure of Example W5, pure 2,6-diisopropyl-4-(2IE 913652 - 16fluorophenoxy)aniline is obtained in the form of colourless crystals of m.p. 82-85°C from 2-fluorophenol and 4-bromo-2,6-diisopropylaniline.

Example W7: 2,6-Diisopropyl-4-(2-chlorophenoxy)phenylisothiocyanate N=C=S A solution of 25 g of 2,6-diisopropyl-4-(2-chlorophenoxy)aniline in 125 ml of dichloromethane are added dropwise, with efficient stirring, to a mixture of 11.4 g of thiophosgene, 120 ml of dichloromethane, 60 ml of water and 18.1 g of ground calcium carbonate. The reaction mixture is stirred for 1 hour at boiling temperature, then cooled and filtered over silica gel. The organic phase is separated, washed with water, dried over sodium sulfate and freed from solvent under vacuum, giving pure 2,6-diisopropyl-4-(2’-chlorophenoxy)phenylisothiocyanate in the form of a yellow oil, nD20 = 1.6130.

Example W8: 2,6-Diisopropyl-4-(2-fluorophenoxy)phenylisothiocyanate N=C=S In accordance with the general procedure of Example W7, pure 2,6-diisopropyl-4-(2fluorophenoxy)phenylisothiocyanate is obtained in the form of a yellow oil, no23 = 1.5979, from 2,6-diisopropyl-4-(2-fluorophenoxy)aniline. - 17Formulation Examples (% = percent by weight) Fl. Emulsifiable concentrates a) b) c) compound W3 25 % 40% 50% calcium dodecylbenzenesulfonate 5 % 8% 6% castor oil polyethylene glycol ether (36 mol of ethylene oxide) 5 % - - tributylphenol polyethylene glycol ether (30 mol of ethylene oxide) - 12% 4% cyclohexanone - 15 % 20% xylene mixture 65 % 25 % 20% Emulsions of any required concentration can be produced from such concentrates by dilution with water. F2. Solutions a) b) c) d) compound W3 80% 10% 5 % 95 % ethylene glycol monomethyl ether 20% - - - polyethylene glycol 400 - 70% - - N-methyl-2-pyrrolidone - 20% - - epoxidised coconut oil - - 1 % 5 % ligroin (boiling range 160-190°) - - 94% - These solutions are suitable for application in the form of microdrops. F3. Granulates a) b) c) d) compound W4 5% 10% 8% 21 % kaolin 94 % - 79% 54% highly dispersed silicic acid 1 % - 13% 7 % attapulgite - 90% - 18% The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently removed by evaporation under vacuum.

F4. Dusts a) b) compound W3 2% 5 % highly dispersed silicic acid 1 % 5 % talcum 97% - kaolin 90 % Ready for use dusts are obtained by intimately mixing the carriers with the active ingredient.

Formulation Examples for solid compounds of formula I (throughout, percentages are by weight) F5. Wettable powders a) b) c) compound Wl 25 % 50% 75 % sodium ligninsulfonate 5 % 5 % - sodium laurylsulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6% 10% octylphenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2% - highly dispersed silicic acid 5 % 10% 10% kaolin 62% 27% - The active ingredient or combination of active ingredients is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

F6. Emulsifiable concentrate compound Wl 10% octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzene sulfonate 3 % castor oil polyglycol ether (36 mol of ethylene oxide) 4 % cyclohexanone 30 % xylene mixture 50 % - 19Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

F7. Dusts a) b) compound W2 5 % 8 % talcum 95 % kaolin - 92 % Ready for use dusts are obtained by mixing the active ingredient with the carrier, and grinding the mixture in a suitable mill.

F8. Extruder granulate compound W1 10% sodium ligninsulfonate 2 % carboxymethyl cellulose 1 % kaolin 87 % The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded, granulated and then dried in a stream of air.

F9. Coated granulate compound W2 3 % polyethylene glycol 200 3 % kaolin 94 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

F10. Suspension concentrate compound W1 40% ethylene glycol 10% nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6% sodium ligninsulfonate 10% % -20carboxymethyl cellulose silicone oil in the form of a 75 % aqueous emulsion water % 32% The finely ground active ingredient or active ingredient combination is homogeneously mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Biological Examples Example BI: Action against Nilaparvata lugens Rice plants are treated with an aqueous emulsion spray formulation containing the test compound in a concentration of 400 ppm. After the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stage. Evaluation is made 21 days later. The percentage reduction in the population (percentage kill) is determined by comparing the number of surviving cicadas on the treated plants with those on the untreated plants.

The compounds of formula are very effective in this test against Nilaparvata lugens. In particular, compounds W2, W3 and W4 are more than 80 % effective.

Example B2: Action against Nephotettix cincticeps Rice plants are treated with an aqueous emulsion spray formulation containing the test compound in a concentration of 400 ppm. After the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stage. Evaluation is made 21 days later. The percentage reduction in the population (percentage kill) is determined by comparing the number of surviving cicadas on the treated plants with those on the untreated plants.

The compounds of formula are very effective in this test against Nephotettix cincticeps. In particular, compounds W2 and W4 are more than 80 % effective.

Example B3: Action against Diabrotica balteata larvae Maize seedlings are sprayed with an aqueous emulsion spray formulation containing 400 ppm of test compound. After the spray coating has dried, the maize seedlings are -21 populated with 10 larvae of Diabrotica balteata in the L2 stage and put into a plastic container. Evaluation is made 6 days later. The percentage reduction in the population (percentage kill) is determined by comparing the number of surviving cicadas on the treated plants with those on the untreated plants.

The compounds of formula are very effective in this test against Diabrotica balteata. In particular, compounds W1 and W2 are more than 80 % effective.

Example B4: Action against Heliothis virescens caterpillars Young soybean plants are sprayed with an aqueous emulsion spray formulation containing 400 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10 caterpillars of Heliothis virescens in the first stage and put into a plastic container. Evaluation is made 6 days later. The percentage reduction of the population and percentage reduction in the feeding damage (percentage kill) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants.

In this test the compounds of formula I are more than 80 % effective against Heliothis virescens.

Example B5: Action against Spodoptera littoralis caterpillars Young soybean plants are sprayed with an aqueous emulsion spray formulation containing 400 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10 caterpillars of Spodoptera littoralis in the third stage and put into a plastic container. Evaluation is made 3 days later. The percentage reduction of the population and percentage reduction in the feeding damage (percentage kill) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants.

In this test the compounds of formula I are more than 80 % effective against Spodoptera littoralis. Compounds W2 and W4 reduce the population by more than 80 % even when used in a concentration of 50 ppm.

Example B6: Action against Aphis craccivora Pea seedlings are infested with Aphis craccivora and then sprayed with a spray mixture containing 400 ppm of test compound and incubated at 20°C. Evaluation is made 3 and 6 -22days later. The percentage reduction in the population (percentage kill) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.

The compounds of formula are very effective in this test against Aphis craccivora. In particular, compounds Wl, W2 and W2 are more than 80 % effective.

Example 7: Systemic action against Nilaparvata lugens Potted rice plants are placed in an aqueous emulsion solution containing 400 ppm of test compound. The rice plants are then populated with larvae in the L2 and L·} stage. Evaluation is made 6 days later. The percentage reduction in the population (percentage kill) is determined by comparing the number of cicadas on the treated plants with those on the untreated plants.

The compounds of formula are very effective in this test against Nilaparvata lugens. In particular, compounds Wl, W2 and W4 are more than 80 % effective.

Example B8: Action against Boophilus microplus Replete adult females are fixed with adhesive tape to a PVC sheet and covered with a cotton wool swab. The test organisms are then treated by impregnating the cotton wool swab with 10 ml of an aqueous solution containing the test compound in a concentration of 125 ppm. The cotton wool swab is then removed and the ticks are incubated for 4 weeks for oviposition. The action against Boophilus microplus is observed either as kill or sterility of the females or takes the form of ovicidal action against the eggs.

In this test the compounds of formula I are more than 80 % effective against Boophilus microplus.

Example B9: Action against Crocidolomia binotalis caterpillars Young cabbage plants are sprayed with an aqueous emulsion spray formulation containing 400 ppm of test compound. After the spray coating has dried, the cabbage plants are populated with 10 caterpillars of Crocidolomia binatolis in the third stage and put into a plastic container. Evaluation is made 3 days later. The percentage reduction in the population and percentage reduction in the feeding damage (percentage kill) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants. -23 In this test the compounds of formula I are more than 80 % effective against Crocidolomia binatolis.

Example BIO: Action against Anthonomus grandis adults Young cotton plants are sprayed with an aqueous emulsion spray formulation containing 400 ppm of test compound. After the spray coating has dried, the cotton plants are populated with 10 adults of Anthonomus grandis and put into a plastic container. Evaluation is made 3 days later. The percentage reduction in the population and percentage reduction in the feeding damage (percentage kill) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants.

In this test the compounds of formula I are very effective against Anthonomus grandis. In particular, compounds W1 and W2 are more than 80 % effective.

Example Bll: Action against Bemisia tabaci Dwarf beans are placed in gauze cages and populated with adults of Bemisia tabaci (white flies). After oviposition, all the adults are removed and 10 days later the plants with the nymphs present thereon are treated with an emulsion spray mixture containing the test compound in a concentration of 400 ppm. Evaluation of the hatching rate is made 14 days after application in comparison with untreated controls.

In this test the compounds of formula I are more than 80 % effective against Anthonomus grandis.

Example B12: Action against Tetranychus urticae Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed to drip point 1 day later with an aqueous emulsion spray formulation containing 400 ppm of test compound. The plants are then incubated for 6 days at 25°C and afterwards evaluated. The percentage reduction in the population (percentage kill) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with those on the untreated plants.

In this test the compounds of formula I are more than 80 % effective against Tetranychus urticae. -24Example Β13: Action against Panonychus ulmi (OP- and carbamate-resistant) Apple seedlings are populated with adult females of Panonychus ulmi. After 7 days the infested plants sprayed to drip point with an aqueous emulsion spray formulation containing 400 ppm of test compound, and then reared in a greenhouse. Evaluation is made 14 days later. The percentage reduction in the population (percentage kill) is determined by comparing the number of dead spider mites on the treated plants with those on the untreated plants.

In this test the compounds of formula I are more than 80 % effective against Panonychus ulmi.

Example B14: Long-term activity against Tetranychus cinnabarinus Potted bean plants in the 2-leaf stage (Autan variety) are sprayed with aqueous emulsion formulations of test compound in concentrations of 100 and 200 ppm. The spray mixtures are obtained by diluting 25 % emulsifiable concentrates with water. After the spray coating has dried, the treated plants are each populated after 2,4, 8 or 16 days with a mixed population of Tetranychus cinnabarinus. The infested plants are kept in a greenhouse at +26°C and 60 % relative humidity and under light for 14 hours per day. The percentage mortality is assessed 9 days after each infestation.

In this test the compounds of formula I are more than 80 % effective against Tetranychus cinnabarinus.

Example B15: Action against Dermanyssus gallinae to 3 ml of a solution containing 100 ppm of test compound and c. 200 mites in different development stages are put into a glass container which is open at the top. The container is then sealed with cotton wool, shaken for 10 minutes until the mites are thoroughly wetted, and then briefly held upside down so that the remainder of the test solution can be absorbed by the cotton wool. A mortality count is made after 3 days.

The compounds of formula are very effective in this test against Dermanyssus gallinae. In particular, compounds W3 and W4 are more than 80 % effective. -25Example BI6: Action against Musca domestica A sugar lump is moistened with a solution of test compound such that, after drying overnight, the concentration of test compound in the sugar is 250 ppm. The treated sugar lump is placed in an aluminium dish together with a moist cotton wool swab and 10 adult (c. 1-week-old) flies [species M. domestica; Schmidlin strain (organophosphate-resistant)]. The dish is then covered with a glass beaker and left for 24 hours at 25°C and 50 % humidity. After this time the mortality rate is determined.

The compounds of formula are very effective in this test. In particular, compound W3 is more than 80 % effective.

Example B17: Comparison tests with known compounds The following compounds are known from the prior art (DE-OS 3034905 und EP-A-175649): compound A: N-2,6-diisopropyl-4-(4-chlorophenoxy)phenyl-N'-tert-butylthiourea N-2,6-dimethyl-4-(4-chlorophenoxy)phenyl-N'-tert-butylcarbodiimide, and N-2,6-dimethyl-4-(4-chlorophenoxy)phenyl-N'-tert-butylcarbodiimide.

The compounds are tested in comparison with compounds Hl, H2, H3 and H4 in the tests of Examples B4, B5 and B9.

Results of the comparison tests Test organism concentration Compound A Compound W1 Compound W2 Heliothis (B4) 400 ppm 35 100 100 200 ppm 0 100 85 100 ppm 0 80 80 Spodoptera (B5) 400 ppm 30 100 100 200 ppm 0 85 100 100 ppm 0 75 100 Crocidolomia (B9) 400 ppm 0 100 100 200 ppm 0 50 75 •27 - Test organism concentration Compound B Compound W3 Compound C Compound W4 Heliothis (B4) 400 ppm 20 100 25 95 200 ppm 0 100 0 70 100 ppm 0 90 0 40 Spodoptera (B5) 400 ppm 0 100 0 100 200 ppm 0 100 0 75 100 ppm 0 100 0 55 Crocidolomia (B9) 400 ppm 0 100 0 100 200 ppm 0 100 0 55

Claims (17)

What is claimed is:

1. A 3,5-diisopropyldiphenyl ether derivative of formula I (I) wherein X is fluoro or chloro and Z is the bridge -NH-CS-NH- or -N=C=N-.

2. A compound according to claim 1, wherein X is chloro.

3. N-2,6-Diisopropyl-4-(2-chlorophenoxy)phenyI-N'-tert-butylthiourea according to claim 1

4. N-2,6-Diisopropyl-4-(2-chlorophenoxy)phenyl-N'-tert-butylcarbodiimide according to claim 1

5. A process for the preparation of a compound of formula I according to claim 1, which comprises a) reacting an isothiocyanate of formula II // \ X (Π) wherein X is as defined for formula I, with tert-butylamine of formula III H 2 N-C(CH 3 ) 3 (ΙΠ) -29to give the thiourea of formula la X CH(CH 3 ) 2 (la) and, if desired, b) converting the thiourea of formula la into the carbodiimide of formula lb CH(CH 3 ) 2 ΛΛ 0 N=C=N ., C(CH 3 ) 3 (lb) X CH(CH 3 ) 2 by removal of hydrogen sulfide.

6. A pesticidal composition which contains as active component at least one 3,5-diisopropyldiphenyl ether derivative of formula I as claimed in claim 1.

7. A composition according to claim 6, which contains at least one carrier in addition to the compound of formula I.

8. A method of controlling insects and representatives of the order Acarina which are injurious to animals and plants, which comprises treating said pests or the locus thereof with a pesticidally effective amount of a 3,5-diisopropyldiphenyl ether derivative of formula I as claimed in claim 1.

9. Use of a 3,5-diisopropyldiphenyl ether derivative of formula I as claimed in claim 1 for controlling noxious insects and representatives of the order Acarina. -3010. Use according to claim 9, wherein the pests are plant-injurious insects.

10. 11. Use according to claim 10, wherein the pests are plant-injurious acarids.

11. 12. A 3,5-diisopropyldiphenyl ether derivative of formula (I) given and defined in claim 1, substantially as hereinbefore described and exemplified.

12. 13. A process for the preparation of a 3,5-diisopropyldiphenyl ether derivative of formula (I) given and defined in claim 1, substantially as hereinbefore described and exemplified.

13. 14. A 3,5-diisopropyldiphenyl ether derivative of formula (I) given and defined in claim 1, whenever prepared by a process claimed in claim 5 or 13.

14. 15. A pesticidal composition according to claim 6, substantially as hereinbefore described and exemplified.

15. 16. A method according to claim 8 of controlling insects, substantially as hereinbefore described.

16.

17. Use according to claim 9, substantially as hereinbefore described.