Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D233/22—Radicals substituted by oxygen atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
  • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
  • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

• the invention relates to new diphenylimidazolines, processes for their preparation and their use for controlling animal pests.
• JP-A 59 1 16660 (cited in CA. 102: 36786); JP-A2 62 195369 (cited in CA.108: 167467) JP-A 04 180944 (cited in CA.118: 23600); US 3,202,674; US 4,066,625; US 4,661,600; WO 93/04045; WO 93/04046; in both phenyl substituted derivatives are disclosed in DOS 27 01 372 (only methyl or ethyl substituent), DOS 32 17 875 (if one among C 6 -C l5 aryl radical, for example, tolyl or xylyl course), the US 4,389,371 and US 4,452,758 (excluding alkali metal salts from N- (alkoxy) alkyl carboxylic acids) and DOS 27 44 782 and EP-AI 596 326 (special heterocyclylmethyl substituent).
• R 1 represents halogen, alkyl, alkoxy or haloalkoxy
• R 2 represents hydrogen, halogen, alkyl or alkoxy
• R 3 , R 4 , R 5 and R 6 each independently represent hydrogen, halogen, alkyl, alkoxy, haloalkyl or haloalkylthio,
• R 7 represents hydrogen, halogen, cyano, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio and
• Y stands for a direct bond, oxygen, methylene, -O-CH 2 - or -CH O- and
• R is cyano, alkoxyalkyl, formyl, alkylcarbonyl, alkoxycarbonyl or
• X represents oxygen or sulfur
• R 8 represents hydrogen or alkyl
• Halogen stands for F, Cl, Br and iodine, in particular for F, Cl and Br.
• the compounds of formula (I) include N-substituted derivatives of the two tautomeric forms of the cyclic imidate function on which the imidazoline is based. These are 1H-4,5-dihydroimidazoles of the formula (I) a and 3H-4,5-dihydroimidazoles of the formula (I) b , which is to be expressed by the dashed line in the formula (I).
• the compounds of the formulas (I) a and (I) b can be present both as mixtures and in the form of the pure isomers and furthermore, depending on the nature of the substituents, as geometric and / or optical isomers or isomer mixtures in different compositions . These isomers can optionally be separated in a conventional manner.
• the invention relates both to the pure isomers and to their mixtures.
• Ar 1 and Ar 2 have the meanings given above and
• R 9 represents C, -C 4 alkyl
• R1-1 o r Fl uor5 chlorine, alkyl, alkoxy or halogenoalkoxy
• R _ 1 represents hydrogen, fluorine, chlorine, alkyl or alkoxy
• R 5_1 and R 6 "1 each independently represent hydrogen, fluorine, chlorine, alkyl, alkoxy, haloalkyl or haloalkylthio and
• Haloalkyl or haloalkylthio can be prepared by using halogen compounds of the formula (Ic)
• Z represents bromine or iodine
• Ar 1 and Ar 2 have the meanings given above,
• X ' represents a leaving group suitable as a function of the radical R, such as -Cl, -Br, -OSO 2 OR 10 or -OR 10 ,
• R 10 represents alkyl or aryl
• Ar 1 , Ar 2 and X have the meanings given above,
• Ar 1 and Ar 2 have the meanings given above,
• the compounds of the formula (I) and their biologically active salts are suitable for controlling animal pests, in particular insects, arachnids and nematodes.
• the new compounds are generally defined by the formula (I). Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below.
• Ar ' preferably stands for the grouping (a)
• Ar 2 preferably represents the groupings (b) or (c)
• R preferably represents cyano, C, -C 4 -alkoxy- C, -C 4 -alkyl, C, -C 4 -alkylcarbonyl, C, -C 4 -alkoxycarbonyl or -C (X) -NHR S.
• R ' preferably represents halogen, C, -C 3 alkyl, C, -C 3 alkoxy or C, -C 3 haloalkoxy.
• R 2 preferably represents hydrogen, halogen, C r C 3 alkyl or C, -C 3 alkoxy.
• R 3 , R ⁇ R 5 and R 6 independently of one another each preferably represent hydrogen, halogen, C r C 2 alkyl or C r 2 alkoxy.
• R 7 preferably represents hydrogen, halogen, cyano, C, -C 6 alkyl, C, -C 6 alkoxy, C, -C 6 alkylthio, C, -C 6 haloalkyl, C, -C 4 haloalkoxy or C, -C 4 haloalkylthio.
• R 8 preferably represents hydrogen or C 1 -C 4 alkyl.
• X preferably represents oxygen or sulfur.
• Y preferably represents a direct bond or oxygen.
• Halogen is preferably F, Cl, Br and iodine, in particular F, Cl and Br.
• Ar particularly preferably represents the groupings (b-a) or (c-a)
• R particularly preferably represents cyano, C, -C 3 -alkoxy-C 1 -C 3 -alkyl, C, -C 3 -alkylcarbonyl, C, -C 2 -alkoxycarbonyl or -C (X) -NHR 8 .
• R 1 particularly preferably represents fluorine, chlorine, bromine, iodine, C, -C 3 - alkyl and C, - C 3 alkoxy.
• R 2 particularly preferably represents hydrogen, fluorine, chlorine, bromine, C, -C 3 -alkyl or C, -C 3 -alkoxy.
• R 3 , R 4 , R 5 and R 6 each independently of one another are particularly preferably hydrogen, fluorine, chlorine, bromine, iodine, C, -C 6 -alkyl or C, -C 6 -alkoxy.
• R 7 particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine, cyano, C, -C 4 -alkyl, C, -C 4 alkoxy, C r C 4 - alkylthio, C, -C substituted by fluorine or chlorine 4 alkyl, C, -C 4 alkoxy or C r C 4 alkylthio.
• R 8 particularly preferably represents hydrogen or C 1 -C 4 -alkyl.
• X particularly preferably represents oxygen or sulfur.
• Ar 2 very particularly preferably represents the groupings (bb) or (cb)
• R very particularly preferably represents cyano, ethoxymethyl, acetyl, propionyl,
• R 1 very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, methoxy or ethoxy.
• R 2 very particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy or ethoxy.
• R 3 , R 4 , R 5 and R 6 each independently of the other very particularly preferably represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert. -Butyl, pentyl, hexyl, methoxy, ethoxy, n- Propoxy, isopropoxy, n-butoxy, isobutoxy, sec.-butoxy, tert.-butoxy, pentyloxy or hexyloxy.
• R 7 very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy,
• R 8 very particularly preferably represents hydrogen, methyl or ethyl.
• X very particularly preferably represents oxygen or sulfur.
• Ar 1 particularly preferably represents the grouping (a-3)
• Ar 2 particularly preferably represents the grouping (bc)
• R 1 and R 2 are the same or different and are particularly preferably hydrogen, F, Cl, CH 3 or ethyl, where R 1 and R 2 are not simultaneously hydrogen.
• R 3 particularly preferably represents bromine, substituted
• Phenyl or phenoxy, -OCF 3 , -SCF 3 or t-butyl are suitable as substituents.
• R particularly preferably represents methyl, ethyl, propyl, i-propyl, cyano,
• Ar 1 very particularly preferably stands for the grouping (a-3)
• Ar 2 very particularly preferably stands for the grouping (bc)
• R 1 and R 2 are the same or different and very particularly preferably represent F, Cl and hydrogen, where R 1 and R 2 do not simultaneously represent hydrogen.
• R 3 very particularly preferably represents bromine or 4-trifluoromethoxyphenyl.
• R very particularly preferably stands for
• Saturated or unsaturated hydrocarbon radicals such as alkyl
• Optionally substituted radicals can be mono- or polysubstituted, whereby in the case of multiple substitutions the substituents can be the same or different.
• Formula (II) provides a general definition of the ⁇ -chlorocarbamates required for carrying out process (A) according to the invention.
• Ar 2 and R 9 preferably have those meanings which have already been mentioned as preferred in connection with the description of the diarylimidazolines of the formula (I).
• ⁇ -chlorocarbamates of the formula (II) can be e.g. produce by adding N, N-dichlorocarbamic acid ethyl ester of the formula (VII) to styrenes of the formula (VIII) in a dipolar aprotic solvent such as acetonitrile at temperatures between -20 and + 20 ° C and the initially formed N-chlorocarbamic acid - Ester halogenated with a reducing agent such as bisulfite solution according to the following reaction scheme:
• N, N-dichlorocarbamic acid ethyl esters of the formula (VII) are commercially available, known from the literature or can be obtained analogously to known processes (see, for example, Thomas A. Foglia, Daniel Swern, J. Org. Chem. 31 (1966) 3625-3631; Ronald E. White, Peter Kovacic, J. Am. Chem. Soc. 97 (1975) 1 180-1184).
• Formula (III) provides a general definition of the benzonitriles required to carry out process (A) according to the invention.
• Ar ' preferably has the meaning which has already been mentioned as preferred in connection with the description of the diarylimidazolines of the formula (I).
• the benzonitriles of the formula (III) and the styrenes of the formula (VIII) are generally known compounds of organic chemistry (see textbooks of organic chemistry such as, for example, Beyer-Walter, textbook of organic chemistry, 21st edition, 1988) and some are commercially available .
• the halogen compounds of the formula (Ic) required to carry out the process (B) according to the invention are a subset of the compounds of the general formula (I) according to the invention and can be prepared, for example, by processes (A), (C) or (D).
• Formula (IV) provides a general definition of the boronic acids required for carrying out process (B) according to the invention.
• R 6 "1 and R 7" 1 preferably have those meanings which have already been mentioned as preferred in connection with the description of the diarylimidazolines of the formula (I), with the exception of bromine and iodine.
• Aromatic boronic acid of the formula (IV) are in some cases commercially available, known from the literature or can be prepared analogously to known methods [cf. Chem. Rev. 45, 2457 (1995); Pure appl. Chem. 66, 213 (1994)].
• Formula (V) provides a general definition of the diarylimidazolines required for carrying out process (C) according to the invention.
• Ar 'and Ar 2 preferably have those meanings which have already been mentioned as preferred in connection with the description of the N-substituted diarylimidazolines of the formula (I).
• the diarylimidazolines of the formula (V) are new and also the subject of the present application.
• Diarylimidazolines of formula (V) can e.g. by preparing carbamates of formula (I-a) with alkali metal hydroxides such as potassium hydroxide in
• the carbamates of the formula (I-a) are a subset of the compounds of the general formula (I) according to the invention and can be prepared, for example, by processes
• N-cyanodiphenylimidazolines of the formula (I-d) required to carry out the process (D) according to the invention are a subset of the compounds of the general formula (I) according to the invention and can be, for example,
• Process (A) according to the invention is carried out in the presence of (aqueous) sulfuric acid. Generally one works at concentrations of 80% to 100%.
• reaction temperature can be varied within a substantial range. In general, temperatures between -20 ° C and + 50 ° C, preferably between 0 and 30 ° C.
• benzonitrile of the formula (III) are generally employed per mol of ⁇ -chlorocarbamate of the formula (II).
• the acid is used in a large, for example 2 to 20 times excess, if appropriate the acid is also used as a solvent.
• Palladium complexes are suitable as catalysts for carrying out process (B) according to the invention.
• Preferred catalysts are, for example, tetrakis (triphenylphosphine) palladium and dichlorobis (triphenylphosphine) palladium.
• Inorganic or organic bases are suitable as acid acceptors for carrying out process (B) according to the invention.
• These preferably include alkaline earth metal or alkali metal hydroxides, acetates, carbonates or hydrogen carbonates, such as, for example, sodium, potassium, barium or ammonium hydroxide, sodium, potassium, calcium or ammonium acetate, sodium, potassium or Am - Monium carbonate, sodium hydrogen or potassium hydrogen carbonate, alkali fluorides, such as cesium fluoride, and tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine , N, N-dimethylaminopyridine, diazabicyclo-octane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
• Suitable diluents for carrying out process (B) according to the invention are water, organic solvents and mixtures thereof.
• examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro, trichloroethane or carbon tetrachloride; Ethers, such as, for example, diethyl, diisopropyl, methyl-t-butyl, methyl-t-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, diethylene glycol dimethyl ether or
• reaction temperature can be varied within a relatively wide range. Generally one works at
• the boronic acid of the formula (IV) and the halogen compound of the formula (Ic) are used in a molar ratio of 1: 1 to 3: 1, preferably 1: 1 to 2: 1.
• the catalyst is generally used from 0.005 to 0.5 mol, preferably from 0.01 mol to 0.1 mol, per mol of the compound of the formula (Ic).
• the base is generally used in excess.
• Process (C) according to the invention is carried out in the presence of a suitable reaction auxiliary.
• All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium, potassium or ammonium hydroxide, sodium amide, lithium diisopropylamide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium, potassium, calcium or ammonium acetate,
• DABCO diazabicyclooctane
• DBN diazabicyclonones
• DBU diazabicycloundecene
• process (C) according to the invention can be carried out in the presence of a suitable phase transfer catalyst.
• suitable phase transfer catalysts are: tetrabutylammonium iodide, bromide or chloride, tributylmethylphosphonium bromide, trimethyl-C 13 / C 15 -alkylammonium chloride or
• Process (C) according to the invention is preferably carried out in the presence of a diluent.
• a diluent for this come water, organic solvents and any mixtures thereof.
• examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro, trichloroethane or carbon tetrachloride; Ethers, such as, for example, diethyl, diisopropyl, methyl-t-butyl, methyl-t-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane,
• reaction temperature can be varied within a relatively wide range. Generally one works at
• Process (D) according to the invention is carried out in the presence of a reaction auxiliary.
• a reaction auxiliary When reacting with hydrogen sulfide, for example, tertiary amines such as pyridine or triethylamine are used. These can also be used as
• Diluents When reacting with water, as aqueous mineral acids such as sulfuric acid or hydrochloric acid, preferably 96% sulfuric acid.
• the acids can also serve as diluents at the same time.
• reaction temperature can be varied within a substantial range. In general, temperatures between -20 ° C and + 100 ° C, preferably between 0 ° C and 60 ° C.
• the amount of hydrogen sulfide or water used in carrying out process (D) according to the invention is not critical. At least one mole of hydrogen sulfide or water is required per mole of nitrile of the formula (I-e). With hydrogen sulfide, it is advantageous to use a larger excess.
• the reactions of the processes (A to D) according to the invention can be carried out under normal pressure or under elevated pressure. Preferably at
• the active substances are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
• animal pests in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
• the pests mentioned above include:
• Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
• Diplopoda for example, Blaniulus guttulatus.
• Chilopoda for example, Geophilus carpophagus and Scutigera spec.
• Thysanura e.g. Lepisma saccharina.
• Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
• Trialeurodes vaporariorum Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
• Buccu- latrix thurberiella Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.
• Conoderus spp. Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
• Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
• Diptera e.g. Aedes spp., Anopheles spp., Culex spp.
• Drosophila melanogaster Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tabanus spp.
• Tannia spp. Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
• Chorioptes spp. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
• Plant-parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.
• the active compounds of the formula (I) according to the invention are notable in particular for outstanding activity against larvae of horseradish leaf beetle (Phaedon cochleariae), caterpillars of the owl butterfly (Spodoptera frugiperda) and all stages of the common spider mite (Tetranychus urticae).
• the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymers
• formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
• organic solvents can also be used as auxiliary solvents.
• auxiliary solvents e.g. organic solvents
• aromatics such as xylene, toluene, or alkylnaphthalenes
• chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
• aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as
• Possible solid carriers are: e.g. Ammonium salts and natural rock flours, such as kaolins, clays,
• Talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and Synthetic rock powders, such as highly disperse silica, aluminum oxide " and silicates, are suitable as solid carriers for granules: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; emulsifiers and / or foaming agents are suitable: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfonates, aryl sulfates as well as protein hydrolyzates; possible dispersants include: lignin s
• Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations.
• Other additives can be mineral and vegetable oils.
• Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt,
• Molybdenum and zinc can be used.
• the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
• the active substance according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
• Insecticides include, for example, phosphoric acid esters, Carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenyl urine, substances produced by microorganisms and others.
• Fenpropimorph fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil,
• Fenamiphos Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxoxinon, Flutoxinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, , Furathiocarb,
• Halofenozide HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene, Imidacloprid, Isazofos, Isofenphos, Isoxathion, Ivermectin, Kernpolyederviruses, Lambda-cyhalothrin, Lufenuron,
• Mecarbam Metaldehyde, Methamidophos, Metharhilic anisopliae, Metharhilic flavoviride, Methidathion, Methiocarb, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos, Naled, Nitenpyramo, Oxidomylonomidamyl, Oxitomyl, Oxitomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl
• Paecilomyces fumosoroseus Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propoxur, Prothiofos, Prothoat, Pyromhrhridosine, Pymmethrofinos, Pymmethrofinos , Pyridathione, pyrimidifen, pyriproxyfen,
• Tefluthrin Temephos, Temivinphos, Terbufos, Tetrachlorvinphos, Thetacypermethrin, Thiapronil, Thiatriphos, Thiocyclam hydrogen oxalate, Thiodicarb,
• Triazophos triazuron, trichlophenidines, trichlorfon, triflumuron, trimethacarb,
• Bacillus thuringiensis strain EG-2348 Bacillus thuringiensis strain EG-2348,
• the active ingredient according to the invention can also be used in its commercially available formulations and in the use forms prepared from these formulations
• Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.
• the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
• the active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
• the application takes place in a customary manner adapted to the application forms
• the active ingredient When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
• the inventive active ingredients act not only against plant, hygiene 'and stored product pests, but also in the veterinary medicine sector against animal parasites (ectoparasites) such as hard ticks, soft ticks, mange mites, mites, flies (biting and licking), parasitic fly larvae, lice, hair lice , Featherlings and fleas.
• animal parasites ectoparasites
• ectoparasites such as hard ticks, soft ticks, mange mites, mites, flies (biting and licking), parasitic fly larvae, lice, hair lice , Featherlings and fleas.
• parasites include:
• Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp ..
• Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp ..
• Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp.
• Siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp ..
• Actinedida Prostigmata
• Acaridida e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodterol spp ., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..
• the active compounds of the formula (I) according to the invention have excellent activity against all larval stages of the Lucillia cuprina fly.
• the active compounds according to the invention are also suitable for controlling arthropods which are used in agricultural animals, such as Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, house birds, aquarium fish and so-called experimental animals, such as Infest hamsters, guinea pigs, rats and mice.
• arthropods By combating these arthropods, deaths and reduced performance (in the case of meat, milk, wool, skins, eggs, honey, etc.) are to be reduced, so that the use of the active compounds according to the invention enables more economical and simple animal husbandry.
• the active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, for example by Injections
• implants through nasal Application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, powdering, and with the aid of shaped articles containing active ingredients, such as collars, ear tags, Tail marks, limb straps, holsters, marking devices, etc.
• active ingredients such as collars, ear tags, Tail marks, limb straps, holsters, marking devices, etc.
• the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or apply after 100 to 10,000-fold dilution or use it as a chemical bath.
• formulations for example powders, emulsions, flowable agents
• insects may be mentioned by way of example and preferably, but without limitation:
• Termites like Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
• Bristle tails such as Lepisma saccharina.
• non-living materials such as preferably plastics, adhesives, glues, papers and cartons, leather, wood and wood processing products and paints.
• the material to be protected against insect infestation is very particularly preferably wood and wood processing products.
• Wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are to be understood as examples: timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone masts, wooden cladding, wooden windows and doors , Plywood, chipboard, carpentry or wood products that are used in general in house construction or joinery.
• the active substances can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
• the formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellants, optionally siccatives and UV stabilizers and, if appropriate Dyes and pigments as well as other processing aids.
• the insecticidal compositions' or concentrates used for protecting wood and wooden materials comprise the active compound according to the invention in a concentration of 0.0001 to 95 wt .-%, in particular 0.001 to 60 wt .-%.
• the amount of the agents or concentrates used depends on the type and the occurrence of the insects and the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
• organic-chemical solvent or solvent mixture and / or an oily or oily or low-volatility organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agents.
• the organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
• Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.
• Mineral oils with a boiling range of 170 to 220 ° C, test gasoline with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C are advantageous.
• Turpentine oil and the like are advantageous.
• the organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture is also a Evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.
• part of the organic chemical solvent or solvent mixture is replaced by an aliphatic polar organic chemical solvent or solvent mixture.
• Aliphatic organochemical solvents containing hydroxyl and / or ester and / or ether groups such as, for example, glycol ethers, esters or the like, are preferably used.
• the known organic-chemical binders are the water-dilutable synthetic resins and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic-chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an Acrylate resin, a vinyl resin, e.g. Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / / or synthetic resin used.
• binders consisting of or containing an Acrylate resin, a vinyl resin, e.g. Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon
• the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous nous substances up to 10 wt .-% can be used. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.
• At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder.
• Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.
• binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
• the plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glycerol glycerol or glycerol ether - Kolether, glycerol ester and p-toluenesulfonic acid ester.
• phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate
• phosphoric acid esters such as tributyl phosphate
• adipic acid esters such as di- (2-ethylhexyl) adipate
• Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
• Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
• a particularly effective wood protection is achieved by industrial impregnation processes, e.g. vacuum, double vacuum or pressure processes.
• the ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.
• insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional admixing partners.
• the compounds mentioned in this document are an integral part of the present application.
• Very particularly preferred mixing partners can be insecticides, such as chlorophyros, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflazazole, as well as traszazole, epaconazole, as well as fungazazole, zonaconazole, as well as Fungazazole, zonaconazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as Fungazazole, as well as
• Example 1-1 Analogously to Example 1-1, 3.1 g (10 mmol) of ethyl N- [2- (4-bromophenyl) -2-chloroethyl] carbamate (for example from Example II-1) and 2.1 g (15 mmol) became 2 -Chlorbenzo- nitrile 2.9 g (72% of theory) 4- (4-bromophenyl) -2- (2-chloro-phenyl) -l-ethoxycarbonyl-4,5-dihydro-lH-imidazole as a colorless, viscous oil receive.
• Example 1-3 Analogously to Example 1-3, 1.5 g (9.0 mmol) of 4- (4-bromophenyl) -2- (2-chlorophenyl) -1-ethoxycarbonyl-4,5-dihydro-1 H-imidazole ( e.g. from example 1-2) and 1.0 g (4.8 mmol) of 4-trifluoromethoxyphenylboronic acid 1.38 g (76% of theory) 2- (2-chlorophenyl) -1-ethoxycarbonyl 1-4 (4'-Trifluoromethoxy-4-biphenylyl) -4,5 -dihydro- 1 H -imidazole obtained as a colorless oil.
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
• Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and with horseradish leaf beetle larvae
• the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
• Example I-7a has a kill rate of 90%.
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
• Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the army worm (Spodoptera frugiperda) while the leaves are still moist.
• the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• Bean plants Phaseolus vulgaris
• Tetranychus urticae which are heavily infested with all stages of the common spider mite (Tetranychus urticae), are immersed in an active ingredient preparation of the desired concentration.
• the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
• Test animals Lucilia cuprina larvae
• test tubes are removed for 2 days and the dolls are counted.
• the effect of the preparation of active substance is assessed according to the number of flies hatched after 1.5 times the development time of an untreated control. 100% means that no flies have hatched; 0% means that all flies hatched normally.

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