US20060100106A1 - Phenyl-substituted 2-enamino-ketonitriles - Google Patents

Phenyl-substituted 2-enamino-ketonitriles Download PDF

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US20060100106A1
US20060100106A1 US11/311,036 US31103605A US2006100106A1 US 20060100106 A1 US20060100106 A1 US 20060100106A1 US 31103605 A US31103605 A US 31103605A US 2006100106 A1 US2006100106 A1 US 2006100106A1
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methyl
alkyl
spp
fluorine
chlorine
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Reiner Fischer
Jutta Bohmer
Ralf Wischnat
Mark Drewes
Peter Dahmen
Rolf Pontzen
Peter Losel
Christoph Erdelen
Dieter Feucht
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/56—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
    • C07C255/43—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms the carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C255/46—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of non-condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C325/00—Thioaldehydes; Thioketones; Thioquinones; Oxides thereof
    • C07C325/02—Thioketones; Oxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/36—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings condensed with one six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention relates to novel phenyl-substituted 2-enamino-ketonitriles, to a plurality of processes for their preparation and to their use as crop protection agents, in particular as herbicides, acaricides, nematicides and insecticides
  • radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials and intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, i.e. including combinations between the given preferred ranges.
  • Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl
  • alkyl or alkenyl can in each case be straight-chain or branched as far as this is possible, including in combination with heteroatoms, such as, for example, in alkoxy.
  • optionally substituted radicals can be mono- or polysubstituted, where in the case of polysubstitution, the substituents can be identical or different.
  • Ar, X are each as defined above, required as starting materials in process (A) are known or can be prepared by processes known in principle from the literature (Organikum, 16th revised edition, pp. 415, 417, VEB Deutscher Verlag dermaschineen, Berlin 1986, German Patent Applications with the application numbers 198 519 86 and 10 007 286 and WO 00/27 812).
  • the compounds of the formula (II) are obtained, for example, by hydrolysing compounds of the formula (XI) in which
  • the compounds of the formula (XI) can be prepared by known processes (Organikum, 16th revised edition, p. 480, VEB Deutscher Verlag dermaschineen, Berlin 1986).
  • the compounds of the formula (XI) are obtained, for example, by reacting compounds of the formula (XII) in which
  • a base for example a metal alkoxide, such as sodium methoxide or sodium ethoxide
  • a diluent for example ether or the alcohol which is derived from the alkoxide
  • halogenating agents for example thionyl chloride, phosgene, phosphorus trichloride
  • a diluent for example optionally chlorinated aliphatic or aromatic hydrocarbons, such as toluene or methylene chloride
  • Cyanoacetic acid esters of the formula (XIII) are known compounds of organic chemistry.
  • B 8 preferably represents hydrogen, hydroxyl, represents in each case optionally cyano-, halogen-, C 1 -C 4 -alkoxy-, C 1 -C 4 -alkylcarbonyl- or C 1 -C 4 -alkoxycarbonyl-substituted C 1 -C 8 -alkyl, C 1 -C 8 -alkylcarbonyl, C 1 -C 8 -alkoxycarbonyl, C 1 -C 8 -alkylthio or C 1 -C 8 -alkylsulphonyl, represents in each case optionally halogen-substituted C 2 -C 6 -alkenyl or C 2 -C 6 -alkinyl, represents in each case optionally halogen- or C 1 -C 4 -alkyl-substituted C 3 -C 8 -cycloalkyl or C 3 -C 8 -cycloalkyl-C 1 -C 4 -
  • novel compounds are obtained, inter alia, by converting compounds of the general formula (XV) in which
  • B 1 represents hydrogen or fluorine
  • Suitable for use as organometallic bases are, in addition to organomagnesium compounds, also organolithium compounds, which are known chemicals for synthesis of organic chemistry.
  • Suitable solvents/diluents are hydrocarbons (such as toluene) or ethers (such as, for example, tetrahydrofuran or diethyl ether). It is also possible to use mixtures of the abovementioned solvents.
  • the reaction temperature is usually between ⁇ 100° C. and 80° C., preferably between ⁇ 80° C. and 25° C. (room temperature).
  • the reaction mixture is diluted with water or an inorganic acid, such as, for example, hydrochloric acid, which may be diluted or concentrated, and the product is isolated using a water-immiscible solvent and purified by customary methods, for example by crystallization.
  • B 1 represents hydrogen or fluorine
  • Bases suitable for use in the reaction are, in addition to alkali metal oxides and alkaline earth metal oxides, tertiary amines, such as triethylamine, pyridine or N,N-diethylaniline, which may be used in molar ratios or else in excess.
  • tertiary amines such as triethylamine, pyridine or N,N-diethylaniline, which may be used in molar ratios or else in excess.
  • Suitable solvents or diluents are, in addition to hydrocarbons such as toluene, also halogenated hydrocarbons, such as dichloromethane. It is possible to use polar aprotic solvents/diluents, such as dimethylformamide, and also mixtures of the abovementioned solvents.
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably between ⁇ 10° C. and 80° C.
  • B 1 represents hydrogen or fluorine
  • Bases suitable for use in the reaction are, in addition to alkali metal oxides and alkaline earth metal oxides, tertiary amines such as triethylamine, pyridine or N,N-diethylaniline, which can be used in molar ratios or else in excess.
  • Suitable solvents are, in addition to hydrocarbons such as toluene, also halogenated hydrocarbons, such as dichloromethane. It is possible to use polar aprotic solvents/diluents, such as dimethylformamide, and also mixtures of the abovementioned solvents.
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably between ⁇ 10° C. and 80° C.
  • W, Y, Z and R 8 are each as defined above,
  • Ar and Hal are each as defined above and X represents cyano
  • Z and Y are each as defined above,
  • arylboronic acids of the formula (X) required for carrying out process E are commercially available, or they can be prepared by known processes.
  • Suitable diluents for process (A) are all organic solvents which are inert towards the reactants. Preference is given to using optionally chlorinated aliphatic or aromatic hydrocarbons, such as toluene, xylene, mesitylene, chlorobenzene, chloroform, methylene chloride, furthermore polar solvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide, dimethylacetamide or N-methylpyrrolidone. It is also possible to use ethers, such as diethyl ether, tetrahydrofuran or dioxane.
  • Bases suitable for use in process (A) are all customary acid acceptors which do not hydrolyse the reactants.
  • tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN) or N,N-dimethylaniline.
  • DABCO diazabicyclooctane
  • DBU diazabicycloundecene
  • DBN diazabicyclononene
  • N,N-dimethylaniline N,N-dimethylaniline.
  • Acids suitable for use in process (A) are all acids which do not hydrolyse the reactants. Preference is given to using organic acids, such as p-toluenesulphonic acid and trifluoroacetic acid.
  • reaction temperatures can be varied within a relatively wide range.
  • the process is expediently carried out at temperatures between ⁇ 20° C. and 160° C., preferably between 0° C. and 120° C.
  • the process (A) is preferably carried out under atmospheric pressure.
  • reaction component of formula (III) is employed in equimolar amounts or in a relatively large excess (up to 5 mol), preferably in 1.5 to 2 times the molar amount, based on the reaction component of the formula (II).
  • the base which is optionally employed is preferably used in an amount which is equimolar to that of the reaction component of the formula (II).
  • the acid that is employed, if appropriate, is preferably used in catalytic amounts.
  • the process (B) is characterized in that compounds of the formula (V) are in each case reacted with thioamides of the formula (VI), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • the starting materials of the formula (V) can be prepared by known processes (Gakhar H. K. et al., J. Indian Chem. Soc. 43 , (1971), 953 or Corsaro A., Heterocycles 23 , (1985), 2645).
  • the compounds of the formula (VI) can be prepared from the corresponding keto compound using thionylating agents, in particular Lawesson's reagent, in inert solvents, such as, for example, toluene (see Preparation Example 5).
  • Diluents suitable for use in the process (B) according to the invention are all solvents which are inert towards the compounds of the formula (V).
  • hydrocarbons such as benzine, benzene, toluene, xylene and tetralin
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene
  • ketones such as acetone and methyl isopropyl ketone
  • furthermore ethers such as diethyl ether, tetrahydrofuran and dioxane
  • carboxylic acid esters such as ethyl acetate
  • strongly polar solvents such as dimethylformamide, N-methylpyrrolidone, dimethyl sulphoxide and sulpholane.
  • Suitable acid binders for the reaction according to process (B) according to the invention are all customary acid acceptors.
  • tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecen
  • Phosphorus reagents suitable for use in the process (B) according to the invention are alkyl phosphites, such as triethyl phosphite, tributyl phosphite, or triphenylphosphines, such as triphenylphosphine.
  • the reaction temperature in the process (B) according to the invention can be varied within a relatively wide range.
  • the process is carried out at temperatures between 0° C. and 200° C., preferably between +20° C. and 150° C.
  • the starting materials of the formula (V) and the thioamide of the formula (VI) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess of one component or the other. Work-up is carried out by customary methods.
  • the process (C) is characterized in that initially compounds of the formula (II) are condensed with orthoesters of the formula (VIII), and the resulting condensates are, without intermediate characterization, reacted with amines of the formula (IX).
  • Acid binders suitable for the reaction according to the process (C) according to the invention are, if appropriate, all customary acid acceptors. Preference is given to using tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base and N,N-dimethylaniline, polymeric bases, such as, for example, disopropylaminopolystyrene, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal carbonates and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.
  • tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diaza
  • Diluents suitable for the process (C) according to the invention are all solvents which are inert towards the orthoesters.
  • hydrocarbons such as benzine, benzene, toluene, xylene and tetralin
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene
  • ketones such as acetone and methyl isopropyl ketone
  • furthermore ethers such as diethyl ether, tetrahydrofuran and dioxane
  • carboxylic acid esters such as ethyl acetate, moreover nitriles such as acetonitrile, and also strongly polar solvents, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulphoxide and sulpholane.
  • dimethylformamide such as benzine, benzene
  • the reaction temperature in the process (C) according to the invention can be varied within a relatively wide range.
  • the process is carried out at temperatures between ⁇ 20° C. and 200° C., preferably between 0° C. and 150° C.
  • the process (C) according to the invention is generally carried out under atmospheric pressure.
  • the starting materials of the formula (II) and the appropriate amine of the formula (IX) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 10 mol, preferably up to 3 mol) of one component or the other.
  • the orthoesters of the formula (VIII) are generally employed in a relatively large excess. Work-up is carried out according to customary methods by concentrating the reaction mixture by removing the diluent and excess reactants under reduced pressure and purifying the residue further.
  • the process (D) is characterized in that compounds of the formula (I) in which Ar, X, Y and Z are each as defined above and K represents oxygen are reacted with sulphurizing agents, if appropriate in the presence of a diluent.
  • the sulphurizing agents to be used are known chemicals for synthesis, such as, for example, phosphorus pentasulphide or 2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiaphosphetane 2,4-disulphide (Lawesson's reagent).
  • Diluents suitable for use in the process (D) according to the invention are all solvents which are inert towards the abovementioned reagents.
  • hydrocarbons such as benzine, benzene, toluene, xylene and tetralin
  • halogenated hydrocarbons such as methylene chloride, chloroform, chlorobenzene and o-dichlorobenzene
  • ethers such as tetrahydrofuran, dioxane, diisopropyl ether or methyl tert-butyl ether.
  • reaction temperatures can be varied within a relatively wide range.
  • the process is carried out at temperatures between 0° C. and 250° C., preferably between 40° C. and 200° C.
  • the starting materials of the formula (I) and the abovementioned reagents are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess of up to 5 mol of the abovementioned reagents. Work-up is carried out by customary methods.
  • arylboronic acids required for carrying out the process (E), such as, for example, 4-chloro-phenylboronic acid, are commercially available, or they can be prepared by known processes.
  • Suitable acid acceptors for carrying out the process (E) according to the invention are inorganic or organic bases. These preferably include alkaline earth metal hydroxides, acetates, carbonates or bicarbonates or alkali metal hydroxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydroxide, potassium hydroxide, barium hydroxide or ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate or ammonium acetate, sodium carbonate, potassium carbonate or ammonium carbonate, sodium bicarbonate or potassium bicarbonate, alkali metal fluorides, such as, for example, caesium fluoride, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, diaza
  • Suitable diluents for carrying out the process (E) according to the invention are water, organic solvents and any mixtures thereof.
  • Examples which may be mentioned are: aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane or tetrachloroethylene; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetra-hydrofuran, 1,2-dimethoxy
  • reaction temperature in the process (E) according to the invention can be varied within a relatively wide range.
  • the process is carried out at temperatures between 0° C. and +200° C., preferably between 50° C. and +150° C.
  • the boronic acid of the formula (X) in which Ar 2′ is as defined above and compounds of the formula (I 1 ) in which Ar 1 , K, X, Y, Z and Hal are each as defined above are employed in a molar ratio of from 1:1 to 3:1, preferably from 1:1 to 2:1.
  • the catalyst is generally employed in amounts of from 0.005 to 0.5 mol, preferably from 0.01 to 0.1 mol, per mole of the compound of the formula (II).
  • the base is generally employed in excess.
  • the active compounds according to the invention are particularly suitable for use as defoliants, desiccants, haulm-killers and, especially, as weed-killers.
  • weeds in the broadest sense, are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
  • the dosages of the active compounds according to the invention required for weed control are between 0.001 and 10 kg/ha, preferably between 0.005 and 5 kg/ha.
  • the active compounds according to the invention can be used, for example, in connection with the following plants:
  • Monocotyledonous crops of the genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.
  • plants are to be understood here all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including plant cultivars which can or cannot be protected by plant breeders' certificates.
  • Parts of plants are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubers and rhizomes.
  • Parts of plants also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.
  • the treatment of the plants and parts of plants according to the invention with the active compounds is carried out directly or by action on their environment, habitat or storage area according to customary treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, brushing-on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multi-layer coating.
  • the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants. With respect to the use of the active compounds according to the invention, particular emphasis is given to the use in connection with transgenic plants since in this case synergistically enhanced activities may be observed.
  • the compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial cultures, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture-land, and for the selective control of weeds in annual crops.
  • perennial cultures for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture-land, and for the selective control of weeds in annual crops.
  • the active compounds according to the invention are highly suitable for the selective control of monocotyledonous weeds in dicotyledonous crops by the pre- and post-emergence method. They can be used very successfully, for example, for the control of harmful grasses in cotton or sugar beet.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound and very fine capsules in polymeric substances.
  • formulations are prepared in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, if appropriate with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
  • Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, mineral or vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or
  • Suitable solid carriers are:
  • suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks;
  • suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable
  • Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs
  • trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the formulations in general contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%, and in addition preferably extenders and/or surfactants.
  • the active compound according to the invention can be present in its commercially available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • active compounds such as insecticides, attractants, sterilizing agents, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • the insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms, inter alia.
  • the active compound according to the invention in its commercial formulations and in the use forms prepared from these formulations, can be present as a mixture with synergists.
  • synergists are compounds which increase the activity of the active compounds without it being necessary for the added synergist to be active itself.
  • the active compound content of the use forms prepared from the commercial formulations can vary within wide ranges.
  • the concentration of active compound in the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
  • the active compounds are furthermore suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene sector. They are active against normally sensitive and resistant species and against all or some stages of development.
  • animal pests preferably arthropods and nematodes, in particular insects and arachnids, which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene sector. They are active against normally sensitive and resistant species and against all or some stages of development.
  • the abovementioned pests include:
  • Isopoda for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber.
  • Chilopoda for example, Geophilus carpophagus and Scutigera spec.
  • Symphyla for example, Scutigerella immaculata.
  • Thysanura for example, Lepisma saccharina.
  • Anoplura for example, Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.
  • Thysanoptera for example, Frankliniella occidentalis, Hercinothrips femoralis, Thrips palmi and Thrips tabaci.
  • From the order of the Homoptera for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vasturix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseu
  • Hymenoptera From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.
  • Acarina for example, Acarus siro, Argas spp., Omithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp. and Brevipulpus spp.
  • the phytoparasitic nematodes include, for example, Pratylenchus spp. Radopholus similis, Ditylenchus dipsaci, Tylenchulus semi penetrans, Heteroderma spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchus spp.
  • the active compounds according to the invention have high insecticidal and acaricidal activity after foliar and soil application.
  • the compounds according to the invention also have fungicidal action. Furthermore, they can also be used as microbicides or antimycotics.
  • the active compound When used against hygiene pests and pests of stored products, the active compound has excellent residual activity on wood and clay, and good stability to alkali on limed substrates.
  • the active compounds according to the invention 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, leaf mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas.
  • animal parasites ectoparasites
  • ectoparasites such as hard ticks, soft ticks, mange mites, leaf mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas.
  • Anoplurida for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.
  • Nematocerina and Brachycerina for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Chrysomyia s
  • Acarapis spp. for example, Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
  • the active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which infest agricultural productive livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese and bees, other pets, such as, for example, dogs, cats, caged birds and aquarium fish, and also so-called test animals, such as, for example, hamsters, guinea pigs, rats and mice.
  • arthropods By controlling these arthropods, cases of death and reduction in productivity (for meat, milk, wool, hides, eggs, honey etc.) should be diminished, so that more economic and easier animal husbandry is possible by use of the active compounds according to the invention.
  • 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, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, such as, for example, by injection (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal administration, by dermal use in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of molded articles containing the active compound, such as collars, ear marks, tail marks, limb bands, halters, marking devices and the like.
  • enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories
  • parenteral administration such as, for example, by injection
  • the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, free-flowing compositions), which comprise the active compounds in an amount of 1 to 80% by weight, directly or after 100- to 10 000-fold dilution, or they can be used as a chemical bath.
  • insects may be mentioned as examples and as preferred - but without a limitation:
  • Hymenopterons such as
  • Kalotermes flavicollis Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus.
  • Industrial materials in the present connection are to be understood as meaning non-living materials, such as, preferably, plastics, adhesives, sizes, papers and cardboards, leather, wood and processed wood products and coating compositions.
  • Wood and processed wood products are materials to be protected, especially preferably, from insect infestation.
  • Wood and processed wood products which can be protected by the agents according to the invention or mixtures comprising these are to be understood as meaning, for example: building timber, wooden beams, railway sleepers, bridge components, boat jetties, wooden vehicles, boxes, pallets, containers, telegraph poles, wood panelling, wooden windows and doors, plywood, chipboard, joinery or wooden products which are used quite generally in house-building or in building joinery.
  • the active compounds can be used as such, in the form of concentrates or in 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 compounds with at least one solvent or diluent, emulsifier, dispersing agent and/or binder or fixing agent, a water repellent, if appropriate siccatives and UV stabilizers and if appropriate dyestuffs and pigments, and also other processing auxiliaries.
  • the insecticidal compositions or concentrates used for the protection of wood and timber products comprise the active compound according to the invention in a concentration of 0.0001 to 95%-by weight, in particular 0.001 to 60% by weight.
  • compositions or concentrates employed depends on the nature and occurrence of the insects and on the medium. The optimum amount employed can be determined for the use in each case by a series of tests. In general, however, it is sufficient to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
  • Solvents and/or diluents which are used are an organochemical solvent or solvent mixture and/or an oily or oil-like organochemical solvent or solvent mixture of low volatility and/or a polar organochemical solvent or solvent mixture and/or water, and if appropriate an emulsifier and/or wetting agent.
  • Organochemical solvents which are preferably used are oily or oil-like solvents having an evaporation number above 35 and a flashpoint above 30° C., preferably above 45° C.
  • Substances which are used as such oily or oil-like water-insoluble solvents of low volatility are appropriate mineral oils or aromatic fractions thereof, or solvent mixtures containing mineral oils, preferably white spirit, petroleum and/or alkylbenzene.
  • Mineral oils having a boiling range from 170 to 220° C., white spirit having a boiling range from 170 to 220° C., spindle oil having a boiling range from 250 to 350° C., petroleum and aromatics having a boiling range from 160 to 280° C., turpentine oil and the like, are advantageously employed.
  • liquid aliphatic hydrocarbons having a boiling range from 180 to 210° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons having a boiling range from 180 to 220° C. and/or spindle oil and/or monochloronaphthalene, preferably ⁇ -monochloronaphthalene, are used.
  • organic oily or oil-like solvents of low volatility which have an evaporation number above 35 and a flashpoint above 30° C., preferably above 45° C., can be replaced in part by organochemical solvents of high or medium volatility, providing that the solvent mixture likewise has an evaporation number above 35 and a flashpoint above 30° C., preferably above 45° C., and that the insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture.
  • organochemical solvent or solvent mixture is replaced by an aliphatic polar organochemical 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.
  • Organochemical binders which are used in the context of the present invention are the synthetic resins and/or binding drying oils which are known per se, are water-dilutable and/or are soluble or dispersible or emulsifiable in the organochemical solvents employed, in particular binders consisting of or comprising an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin, such as indene-cumarone resin, silicone resin, drying vegetable oils and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.
  • binders consisting of or comprising an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin
  • the synthetic resin used as the binder can be employed in the form of an emulsion, dispersion or solution.
  • Bitumen or bituminous substances can also be used as binders in an amount of up to 10% by weight.
  • Dyestuffs, pigments, water-repelling agents, odour correctants and inhibitors or anticorrosive agents and the like which are known per se can additionally be employed.
  • composition or concentrate to comprise, as the organochemical binder, at least one alkyd resin or modified alkyd resin and/or one drying vegetable oil.
  • Alkyd resins having 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 evaporation of the active compounds and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder employed).
  • the plasticizers originate 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, glycerol ethers or higher molecular weight glycol ethers, glycerol esters and p-toluenesulphonic acid esters.
  • 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 based chemically on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl ether or ketones, such as benzophenone or ethylenebenzophenone.
  • Possible solvents or diluents are, in particular, also water, if appropriate as a mixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersing agents.
  • the ready-to-use compositions can also comprise other insecticides, if appropriate, and also one or more fungicides, if appropriate.
  • Possible additional mixing components are, preferably, the insecticides and fungicides mentioned in WO 94/29 268.
  • the compounds mentioned in this document are an explicit constituent of the present application.
  • insecticides such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron
  • fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.
  • the active compounds according to the invention can be used particularly effectively for controlling plant-damaging insects, such as, for example, against the larvae of the mustard beetle (Phaedon cochleariae), against the larvae of the green rice leafhopper (Nephotettix cincticeps) and against the larvae of the green peach aphid (Myzus persicae).
  • plant-damaging insects such as, for example, against the larvae of the mustard beetle (Phaedon cochleariae), against the larvae of the green rice leafhopper (Nephotettix cincticeps) and against the larvae of the green peach aphid (Myzus persicae).
  • a fungicidal activity of the active compounds according to the invention is noticeable.
  • a broad fungicidal effect can be observed.
  • the active compounds are, in particular, also suitable for controlling mildew, leaf blotch and Fusaria on the infected plants.
  • reaction mixture is concentrated using a rotary evaporator, and the product that has been formed is extracted using methylene chloride/NaHCO 3 solution.
  • the compounds contained in the solution were separated by column chromatography on a silica gel phase using the mobile phase hexane/ethyl acetate (2:1).
  • the components contained in the mixture were separated by column chromatography on a silica gel phase using the mobile phase hexane/ethyl acetate (10:1).
  • the compounds contained in the mixture are separated by column chromatography on a silica gel phase using the mobile phase hexane/ethyl acetate (2: 1).
  • Me denotes a methyl group (CH 3 ).
  • Post-Emergence Test Solvent 5 parts by weight of acetone
  • 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, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Test plants of a height of 5-15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. After 3 weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
  • the compounds of Preparation Examples I-a-35, I-a-20, I-a-4, I-a-17, I-a-3, I-a-59, I-a-58, I-a-29, I-a-8 and I-a-23 exhibit strong activity against weeds, and some are tolerated well by crop plants, such as, for example, wheat.
  • Pre-Emergence Test Solvent 5 parts by weight of acetone
  • 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, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of active compound.
  • the amount of water per unit area is advantageously kept constant.
  • the concentration of active compound in the preparation is immaterial, only the application rate of active compound per unit area matters.
  • the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
  • the compounds of Preparation Examples I-a-3, I-a-17, I-a-20, I-a-4, I-a-58, I-a-59, I-a-23, I-a-8 and I-a-21 exhibit strong activity against weeds, and some are tolerated well by crop plants, such as, for example, wheat and soya.
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Containers are filled with sand, solution of active compound, Meloidogyne incognita egg/larvae suspension and lettuce seeds.
  • the lettuce seeds germinate and the plants develop. On the roots, galls are formed.
  • the nematicidal action is determined in % using gall formation as a measure. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to that on the untreated control.
  • Phaedon Larvae Test Solvent 30 parts by weight of dimethylformamide
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Cabbage leaves Brassica oleracea
  • Cabbage leaves Brassica oleracea
  • active compound of the desired concentration are treated by being dipped into the preparation of active compound of the desired concentration and are populated with larvae of the mustard beetle ( Phaedon cochleariae ) while the leaves are still moist.
  • the kill in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
  • Plutella Test Solvent 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Cabbage leaves Brassica oleracea
  • Cabbage leaves Brassica oleracea
  • the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Cabbage leaves Brassica oleracea
  • Cabbage leaves Brassica oleracea
  • active compound of the desired concentration are populated with caterpillars of the armyworm ( Spodoptera frugiperda ) while the leaves are still moist.
  • the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Bean plants Phaseolus vulgaris ) which are heavily infested by all stages of the greenhouse red spider mite ( Tetranychus urticae ) are dipped into a preparation of active compound of the desired concentration.
  • the effect in % is determined. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.

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Abstract

The present invention relates to novel phenyl-substituted 2-enamino-ketonitriles of the formula (I):
Figure US20060100106A1-20060511-C00001
 in which Ar, X, Z, Y and K are each as defined in the description, to a plurality of processes for their preparation and to their use as herbicides and pesticides.

Description

  • The invention relates to novel phenyl-substituted 2-enamino-ketonitriles, to a plurality of processes for their preparation and to their use as crop protection agents, in particular as herbicides, acaricides, nematicides and insecticides
  • Certain 2-enamino-ketonitriles which are substituted on the phenyl ring and have herbicidal action have already been disclosed, for example in EP-A 0 348 002. However, these 2-[3-phenoxy- or 3-[(2-pyridyloxy)benzoyl]-3-(dialkylamino)acrylo-nitriles have hitherto not attained any importance.
  • Likewise without any significant importance are the compounds with herbicidal properties disclosed in JP-A2 10 175 937, WO 99/16753 and EP-A 0 490 220.
  • Furthermore, 2-enamino-ketonitriles have been disclosed for use as intermediates for the synthesis of antibacterial active compounds, see DE-A 35 02 935, EP-A 0 220 523, DE 34 26 483 and EP-A 0 168 737.
  • Further 2-enamino-ketonitriles are also known from DE-A 19 958 164, DE-A 19 851 986, DE-A 10 007 286 and WO 00/27812.
  • Also known are 2-enamino-ketonitriles which are unsubstituted on the phenyl ring (I. N. Sobhy, H. S. Zahi, M. M. Hassan, E. M. Hilmy, (Chem. Ind. (London), 1988, 17, 563-564), I. N. Sobhy, M. M. Hassan, E. M. Hilmy (Arch. Pharm. 1987, 320 (6), 487-491), E. A. Ghani, M. A. Fathy, F. A. Amer, Collet. Czech, Chem. Commun. (1986, 51, 2193-2198), C. Degrand, G. Belot, P-L. Compagnon, F. Jasquez, Can. J. Chem. (1983, 61, 2581-2589), E. M. Hilmy, M. S. Fahmy, E. A. A. Hafez, R. M. Elmoghayar J. Heterocyl. Chem. (1979, 16, 1109-1111), H. Schäfer, K. Gewald, Monatsh. Chem. (1978), 109, 527-535). M. Savkar, S. Chattopadhyay, K. K. Mahalanabis, Ind. J. Chem. Sect. B (1996, 25 B, 1133-1137). Z. E. S. Kandeel, F. M. Abelrazeh, M. E. Eldin, J. Chem. Soc. Perk. Trans. 1 (1985, 7, 1499-1501), H. Jurek, H. W. Schmidt, G. Gfrerer, Synthesis, (1982, 9, 791) K. Gewald, H. Schäfer, K. Sattler, Monatsh. Chem. (1979, 110, 1189).
  • However, a use of these compounds as crop protection agents has hitherto not been described.
  • The formula (I) provides a general definition of the novel 2-enamino-ketonitriles
    Figure US20060100106A1-20060511-C00002
    in which
    • K represents oxygen or sulphur,
    • Ar represents in each case optionally substituted phenyl, naphthyl, represents in each case optionally substituted mono- or bicyclic hetaryl having 5 to 10 ring atoms, or represents the group
      Figure US20060100106A1-20060511-C00003
      where
      • B1 represents hydrogen or halogen,
      • two adjacent radicals—B2 and B3 or B3 and B4—together represent one of the groupings below
      • -Q1-CQ2-, -Q1-CQ2-Q3-, -Q1-C(B6,B7)-Q3-, -C(B6,B7)-CQ2-,
      • —C(B6B7)-Q1-CQ2-, -Q1-C(B6,B7)—C(B6,B7)-,
      • -Q1-C(B6B7)—C(B6,B7)-Q3-, —C(B6,B7)—C(B6,B7)-CQ2-,
      • -Q1-C(B6)═C(B6)—, —C(B6)═C(B6)-CQ2-, -Q1-C(B6,B7)-CQ2-,
      • —N(B8)—C(B6,B7)-CQ2-, —C(B6)═N—, -Q1-CQ2-C(B6,B7)—,
      • -Q1-CQ2-N(B8)-, -Q1-C(B6,B7)-CQ2-N(B8)—,
      • —C(B6,B7)-Q1-CQ2-N(B8)—, —C(B6,B7)—C(B6,B7)—N(B8)—,
      • —-C(B6,B7)—C(B6,B7)-CQ2-N(B8)—, —C(B6)═C(B6)—N(B8)—,
      • —C(B6)═C(B6)-CQ2-N(B8)—, —C(B6,B7)-CQ2-N(B8)—,
      • —N(B8)—C(B6,B7)-CQ2-N(B8)—, —C(B6)═N—N(B8)—,
      • -Q1-CQ2-C(B6,B7)—N(B8)—, -Q1-C(B6,B7)—C(B6,B7)-CQ2-N(B8)—,
      • —N(B8)-CQ2-C(B6)═N—, -Q1-C(B6)═C(B6)-Q3-,
      • —N(B8)—C(B6)═C(B6)-CQ2-,
      • —N(B8)C(B6)═N—, —N(B8)—C(B6,B7)—C(B6,B7)-Q3-,
      • —N(B8)-CQ2-C(B6,B7)-Q4-, —N(B8)-CQ2-CQ2-Q3-,
      • -Q1-C(B6)═C(B6)—C(B6,B7)—, -Q1-C(B6)═C(B6)—,
      • and the fourth radical, B4 or B2, represents hydrogen, thiocarbamoyl, cyano or halogen,
      • where
      • Q1, Q2 and Q3 are identical or different and each represent oxygen or sulphur, and
      • Q4 represents —SO— or —SO2—,
      • B6 and B7 are identical or different and individually represent hydrogen, halogen or alkyl or together represent alkanediyl, and
      • B8 represents hydrogen, hydroxyl, represents in each case optionally cyano-, halogen-, alkoxy-, alkylcarbonyl- or alkoxycarbonyl-substituted alkyl, alkylcarbonyl, alkoxycarbonyl, alkylthio or alkylsulphonyl, represents in each case optionally halogen-substituted alkenyl or alkinyl, represents in each case optionally halogen- or alkyl-substituted cycloalkyl or cycloalkylalkyl, represents in each case optionally halogen-substituted alkoxy or alkenyloxy, represents in each case optionally cyano-, halogen-, alkyl-, halogenoalkyl-, alkoxy- or halogenoalkoxy-substituted arylalkyl or arylalkoxy,
    • X represents CN,
      Figure US20060100106A1-20060511-C00004
    • Y represents hydrogen, represents in each case optionally substituted alkyl, alkenyl, alkinyl, alkoxyalkyl, alkylthioalkyl, represents in each case optionally substituted cycloalkyl or cycloalkylalkyl which are in each case optionally interrupted in the cycle by heteroatoms, or represents in each case optionally substituted phenylalkyl or hetarylalkyl,
    • Z represents hydrogen, represents in each case optionally substituted alkyl, phenyl or phenylalkyl,
    • R1 represents hydrogen, represents in each case optionally substituted saturated or unsaturated alkyl or cycloalkyl, each of which is optionally interrupted by heteroatoms, represents in each case optionally substituted phenyl or hetaryl, represents in each case optionally substituted phenylalkyl or hetarylalkyl, and
    • R2 represents hydrogen, represents in each case optionally substituted saturated or unsaturated alkyl or alkoxy, represents in each case optionally substituted phenyl, phenylalkyl or phenylalkyloxy, or
    • R1, R2 furthermore together with the nitrogen atom to which they are attached represent an optionally substituted cycle which is optionally substituted by a plurality of heteroatoms.
  • For the compounds of the formula (I), the following applies:
    • Ar preferably represents Ar1, where Ar1 represents phenyl, naphthyl or mono- or bicyclic hetaryl having five to ten ring atoms, each of which radicals is optionally mono- to pentasubstituted by halogen, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkinyl, C1-C8-alkoxy, C2-C8-alkenyloxy, C3-C8-alkinyloxy, C1-C8-alkylthio, C1-C6-alkylsulphonyl, C1-C6-halogenoalkyl, C1-C6-halogenoalkoxy, C2-C8-halogenoalkenyloxy, C1-C2-alkylidenediyl-dioxy, C1-C2-halogenoalkylidenediyl-dioxy, halogeno-C1-C4-alkylthio, halogeno-C1-C4-alkylsulphonyl, phenyl-C1-C4-alkoxy, hydroxyl, mercapto, nitro, cyano, amino or by the groups
      Figure US20060100106A1-20060511-C00005
    •  or represents Ar2, where Ar2 represents Ar1 which is additionally substituted by phenyl, naphthyl, five- or six-membered hetaryl, phenyl-C1-C4-alkyl, phenoxy, phenyl-S(O)g-, five- or six-membered hetaryloxy or hetaryl-S(O)g, where these substituents for their part are in each case optionally mono- to tetrasubstituted by halogen, C1-C6-alkyl, C1-C6-alkenyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, nitro or cyano, where g represents 0, 1 or 2,
      • or represents the group
        Figure US20060100106A1-20060511-C00006
      • where
      • B1 represents hydrogen or halogen,
      • two adjacent radicals—B2 and B3 or B3 and B4—together represent one of the groupings below
      • -Q1-CQ2-N(B8)—, -Q1-C(B6,B7)-CQ2-N(B8)—,
      • —N(B8)—C(B6,B7)-CQ2-N(B8)—, -Q1-CQ2-C(B6,B7)—N(B8)—,
      • -Q1-C(B6)═C(B6)—C(B6,B7)—, -Q1-C(B6)═C(B6)—,
      • —N(B8)-CQ2-C(B6)═N—
      • where
      • Q1 and Q2 are identical or different and each represent oxygen or sulphur,
      • B6 and B7 are identical or different and individually represent hydrogen or methyl,
      • B8 represents hydrogen, hydroxyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, acetyl-, propionyl-, methoxycarbonyl- or ethoxycarbonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, represents in each case optionally fluorine- and/or chlorine-substituted methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, propenyloxy or butenyloxy, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl-, ethyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy- or trifluoromethoxy-substituted benzyl or benzyloxy,
      • and the fourth radical, B4 or B2, represents hydrogen, cyano, fluorine or chlorine,
    • K preferably represents oxygen or sulphur.
    • L preferably represents oxygen or sulphur.
    • X preferably represents CN,
      Figure US20060100106A1-20060511-C00007
    • Y preferably represents hydrogen, in each case optionally mono- or polyhydroxy-substituted C1-C12-alkyl, C3-C10-alkenyl, C3-C10-alkinyl, C1-C6-alkoxy-C2-C4-alkyl, di-C1-C6-alkoxy-C2-C4-alkyl, C1-C6-alkoxy-C2-C4-cyanoalkyl, C1-C6-alkylthio-C2-C4-alkyl, C1-C8-halogenoalkyl, C1-C8-halo-genoalkenyl or C1-C8-cyanoalkyl, represents in each case optionally C1-C6-alkyl-, C1-C6-alkoxy-, C1-C4-halogenoalkyl-, cyano-, halogenophenyl-, benzyl-, C1-C6-hydroxyalkyl- or halogen-substituted C3-C8-cycloalkyl or C3-C8-cycloalkyl-C1-C4-alkyl which are optionally interrupted in the cycle by oxygen, sulphur or nitrogen, represents phenyl-C1-C4-alkyl or five- or six-membered hetaryl-C1-C4-alkyl, each of which is optionally mono- to tetra-substituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, cyano or nitro.
    • Z preferably represents hydrogen, C1-C6-alkyl, represents phenyl or phenyl-C1-C4-alkyl, each of which is optionally mono- to trisubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, nitro or cyano.
    • R1 preferably represents hydrogen, represents in each case optionally fluorine- and/or chlorine-substituted C1-C10-alkyl, C3-C10-alkenyl, C3-C6-alkinyl, represents in each case optionally fluorine-, chlorine-, C1-C4-alkyl-, C1-C4-alkoxy-substituted C3-C8-cycloalkyl or C5-C8-cycloalkenyl in which optionally one methylene group may be replaced by oxygen or sulphur, or represents phenyl, pyridyl, thienyl, pyrimidyl, thiazolyl, phenyl-C1-C4-alkyl, pyridyl-C1-C2-alkyl, thiazolyl-C1-C2-alkyl, each of which is optionally mono- to tetrasubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, cyano or nitro.
    • R2 preferably represents hydrogen, C1-C6-alkyl or C3-C6-alkenyl.
    • R1, R2 preferably furthermore together with the nitrogen atom to which they are attached represent an in each case optionally C1-C4-alkyl-substituted five- to eight-membered cycle in which optionally one methylene group may be replaced by oxygen or sulphur.
    • R3 preferably represents in each case optionally fluorine- and/or chlorine-substituted C1-C10-alkyl, C2-C10-alkenyl, C3-C10-alkinyl, C1-C10-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, in each case optionally fluorine-, chlorine-, C1-C4-alkyl-, C1-C4-alkoxy-substituted C3-C8-cycloalkyl or C3-C8-cycloalkoxy in which optionally one methylene group may be replaced by oxygen or sulphur, represents phenyl, phenoxy, benzyloxy, five- or six-membered hetaryl or phenyl-C1-C4-alkyl, each of which may optionally be mono- to tetrasubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, cyano or nitro, or, in the case of the radicals a), c) and f) mentioned under Ar, also represents a group
      Figure US20060100106A1-20060511-C00008
    • R4 preferably represents hydrogen or C1-C4-alkyl.
    • R5 preferably represents hydrogen or optionally fluorine- and/or chlorine-substituted C1-C4-alkyl.
    • R6 preferably represents hydrogen, in each case optionally fluorine- and/or chlorine-substituted C1-C10-alkyl, C3-C8-alkenyl, C3-C8-alkinyl, C1-C10-alkoxy, C3-C8-alkenyloxy, optionally fluorine-, chlorine-, C1-C4-alkyl- or C1-C4-alkoxy-substituted C3-C8-cycloalkyl in which optionally one methylene group may be replaced by oxygen or sulphur, represents phenyl, phenyl-C1-C4-alkyl or phenyl-C1-C2-alkoxy, each of which may optionally be mono- to tetrasubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, cyano or nitro.
    • R7 preferably represents hydrogen, C1-C6-alkyl or C3-C6-alkenyl.
    • R6, R7 preferably furthermore together with the nitrogen atom to which they are attached represent an optionally C1-C4-alkyl-substituted five- to eight-membered cycle in which optionally one methylene group may be replaced by oxygen or sulphur.
    • K particularly preferably represents oxygen or sulphur.
    • Ar particularly preferably represents Ar1, where Ar1 represents phenyl, naphthyl, quinolinyl, thienyl, pyrimidyl, furanyl, thiazolyl, benzothiazolyl, oxazolyl, pyrazolyl or pyridyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkinyloxy, C1-C6-alkylthio, C1-C4-alkyl-sulphonyl, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, C2-C4-halogeno-alkenyloxy, C1-C2-alkylidenediyl-dioxy, C1-C2-halogenoalkylidenediyl-dioxy, halogeno-C1-C2-alkylthio, halogeno-C1-C2-alkylsulphonyl, phenyl-C1-C4-alkoxy, hydroxyl, mercapto, nitro, cyano, amino or by one of the groups below
      Figure US20060100106A1-20060511-C00009
    •  or represents Ar2, where Ar2 represents Ar1 which is additionally substituted by phenyl, pyridyl, pyrimidyl, thienyl, furanyl, thiazolyl, tetrazolyl, triazolyl, benzyl, phenoxy, phenyl-S(O)g-, pyridyloxy, pyrimidyloxy, thiazolyloxy, pyridyl-S(O)g-, pyrimidyl-S(O)g- or thiazolyl-S(O)g-, where these substituents for their part are optionally mono- to trisubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C2-C4-alkenyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, nitro or cyano, where g represents 0, 1 or 2,
      • or represents the group
        Figure US20060100106A1-20060511-C00010
      • where
      • B1 represents hydrogen or halogen,
      • two adjacent radicals—B2 and B3 or B3 and B4—together represent the grouping below
      • -Q1-C(B6,B7)-CQ2-N(B8)—,
      • where
      • Q1 and Q2 are identical or different and each represents oxygen or sulphur,
      • B6 and B7 are identical or different and individually represent hydrogen or methyl,
      • B8 represents hydrogen, hydroxyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, acetyl-, propionyl-, methoxycarbonyl- or ethoxycarbonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, represents in each case optionally fluorine- and/or chlorine-substituted methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, propenyloxy or butenyloxy, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl, ethyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy- or trifluoromethoxy-substituted benzyl or benzyloxy,
      • and the fourth radical, B4 or B2, represents hydrogen, cyano, fluorine or chlorine,
    • X particularly preferably represents CN,
      Figure US20060100106A1-20060511-C00011
      • Y particularly preferably represents hydrogen, represents in each case optionally mono- or poly-hydroxy-substituted C1-C10-alkyl, C1-C6-halogenoalkyl, C3-C8-alkenyl, C3-C8-alkinyl, C1-C4-alkoxy-C2-C3-alkyl, di-C1-C4-alkoxy-C2-C4-alkyl, C1-C4-alkoxy-C2-C4-cyanoalkyl, C1-C4-alkylthio-C2-C3-alkyl, C1-C6-halogenoalkenyl or C1-C6-cyanoalkyl, represents in each case optionally C1-C4-alkyl-, C1-C4-alkoxy-, C1-C2-halogenoalkyl-, cyano-, halogenophenyl-, benzyl-, C1-C4-hydroxyalkyl-. fluorine- or chlorine-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C2-alkyl in which optionally one methylene group may be replaced by oxygen or nitrogen, represents phenyl-C1-C3-alkyl, thiazolylmethyl, triazolylmethyl or pyridylmethyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, cyano or nitro.
    • Z particularly preferably represents hydrogen, C1-C3-alkyl, represents phenyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, nitro or cyano.
    • R1 particularly preferably represents hydrogen, represents in each case optionally fluorine and/or chlorine-substituted C1-C6-alkyl, C2-C6-alkenyl, C3-C4-alkinyl, represents optionally fluorine-, chlorine-, C1-C2-alkyl-, C1-C2-alkoxy-substituted C3-C6-cycloalkyl or represents phenyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, cyano or nitro.
    • R2 particularly preferably represents hydrogen, represents C1-C4-alkyl or C3-C4-alkenyl, each of which is optionally substituted by fluorine and/or chlorine.
    • R1,R2 particularly preferably furthermore together with the nitrogen atom to which they are attached represent an optionally methyl-substituted five- or six-membered cycle in which optionally one methylene group may be replaced by oxygen,
    • R3 particularly preferably represents in each case optionally fluorine- and/or chlorine-substituted C1-C6-alkyl, C2-C6-alkenyl, C3-C6-alkinyl, C1-C6-alkoxy, C1-C4-alkoxy-C1-C2-alkyl, C1-C4-alkylthio-C1-C2-alkyl, in each case optionally fluorine-, chlorine-, C1-C2-alkyl- and/or C1-C2-alkoxy-substituted C3-C6-cycloalkyl or C3-C6-cycloalkoxy in which optionally one methylene group may be replaced by oxygen, represents phenyl, phenoxy, benzyloxy, thienyl, furanyl, pyridyl, pyrimidyl, thiazolyl, pyrazolyl or phenyl-C1-C2-alkyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro, or, in the case of the radicals a), c) and f) mentioned under Ar, also represents a group
      Figure US20060100106A1-20060511-C00012
    • R4 particularly preferably represents hydrogen.
    • R5 particularly preferably represents hydrogen, methyl or ethyl.
    • R6 particularly preferably represents hydrogen, in each case optionally fluorine- and/or chlorine-substituted C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkinyl, C1-C6-alkoxy, C3-C6-cycloalkyl, in which optionally one methylene group may be replaced by oxygen, represents phenyl or phenyl-C1-C2-alkyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro.
    • R7 particularly preferably represents hydrogen or C1-C4-alkyl.
      • R6, R7 particularly preferably furthermore together with the nitrogen atom to which they are attached represent an optionally C1-C2-alkyl-substituted five- or six-membered cycle in which optionally one methylene group may be replaced by oxygen.
    • K very particularly preferably represents oxygen and sulphur.
    • Ar very particularly preferably represents Ar1, where Ar1 represents phenyl which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, s-, n-, i- or t-butyl, methoxy, ethoxy, propoxy, i-propoxy, s-, n-, i- or t-butoxy, allyloxy, methallyloxy, 2-butenyloxy, propargyloxy, 2-butinyloxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylenedioxy, difluoromethylenedioxy, tetrafluoroethylenedioxy, difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, benzyloxy, hydroxyl, mercapto, nitro, cyano or amino, or represents pyridyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, methylthio, ethylthio or trifluoromethyl,
      • or represents Ar2, where Ar2 represents Ar1 which is additionally substituted by phenyl, pyridyl, thienyl, tetrazolyl, triazolyl or phenoxy, where these substituents are for their part optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, s-, n-, i- or t-butyl, methoxy, ethoxy, i-propoxy, s-, n- or t-butoxy, trifluoromethyl, trifluoromethoxy, nitro or cyano,
      • or represents the group
        Figure US20060100106A1-20060511-C00013
      • where B1 represents hydrogen or fluorine and B8 represents allyl, propargyl or benzyl,
    • X very particularly preferably represents
      Figure US20060100106A1-20060511-C00014
    • Y very particularly preferably represents hydrogen, in each case optionally mono- or poly-hydroxy-substituted C1-C6-alkyl, C1-C4-halogenoalkyl, C3-C6-alkenyl, C3-C6-alkinyl, C1-C4-alkoxy-C2-C3-alkyl, di-C1-C2-alkoxy-C2-C4-alkyl, C1-C2-alkoxy-C2-C4-cyanoalkyl, C1-C2-alkylthio-C2-C3-alkyl, C1-C5-halogenoalkenyl or C1-C6-cyanoalkyl, represents in each case optionally methyl-, methoxy-, ethoxy-, trifluoromethyl-, cyano-, chlorophenyl-, benzyl-, hydroxymethyl-, fluorine- or chlorine-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C2-alkyl in which optionally one methylene group may be replaced by oxygen or sulphur, represents benzyl, phenethyl or pyridylmethyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro.
    • Z very particularly preferably represents hydrogen, methyl, ethyl, represents phenyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro.
    • R3 very particularly preferably represents methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl, vinyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, n-, s-, i- or t-butyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cyclopentyloxy, cyclohexyloxy, represents phenyl, pyridyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, n-, s-, i- or t-butyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro, or in the case of the radicals a), c) and f) mentioned Ar, also represents the group
      Figure US20060100106A1-20060511-C00015
    • R5 very particularly preferably represents hydrogen or methyl.
    • R6 very particularly preferably represents hydrogen, methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, represents phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro
    • R7 very particularly preferably represents hydrogen, methyl or ethyl.
    • R6, R7 together with the nitrogen atom to which they are attached very particularly preferably represent a pyrrolidine, piperidine or morpholine radical.
    • K especially preferably represents oxygen.
    • Ar especially preferably represents Ar1, where Ar1 represents phenyl which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl, methoxy, ethoxy, propoxy, isopropoxy, n-, s-, i- or t-butoxy, allyloxy, methallyloxy, 2-butenyloxy, propargyloxy, 2-butinyloxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylenedioxy, difluoro- methylenedioxy, tetrafluoroethylenedioxy, difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, benzyloxy, hydroxyl, nitro, mercapto, cyano or amino, or represents pyridyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, propoxy, i-propoxy or trifluoromethyl,
    •  or represents Ar2, where Ar2 represents Ar1 which is additionally substituted by phenyl or phenoxy, where these substituents for their part are optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, n-, s-, i- or t-butyl, methoxy, ethoxy, isopropoxy, n-, s-, i- or t-butoxy, trifluoromethyl, trifluoromethoxy, nitro or cyano.
    • Ar most preferably represents phenyl which is mono- or polysubstituted by trifluoromethyl, fluorine, chlorine, allyloxy, cyano, benzyloxy, or represents the group
      Figure US20060100106A1-20060511-C00016
    •  where particular emphasis is given to the meanings 4-chlorophenyl, 3,5-di(trifluoromethyl)phenyl and 2-fluoro-4-chloro-5-allyloxy.
    • X especially preferably represents CN.
    • Y especially preferably represents hydrogen, C1-C6-alkyl, C1-C3-halogeno-alkyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl.
    • Z especially preferably represents hydrogen or methyl.
      Particular mention may also be made of the following sub-group of compounds of the formula (I):
  • 2-enamino-ketonitriles of the general formula (I)′,
    Figure US20060100106A1-20060511-C00017
    in which
    • K represents oxygen or sulphur,
    • Ar represents in each case substituted phenyl, naphthyl or represents in each case optionally substituted mono- or bicyclic hetaryl having 5 to 10 ring atoms,
    • X represents
      Figure US20060100106A1-20060511-C00018
    • Y represents hydrogen, represents in each case optionally substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, represents in each case optionally substituted cycloalkyl or cycloalkylalkyl which is interrupted in the cycle by heteroatoms or represents optionally substituted phenylalkyl or hetarylalkyl,
    • Z represents hydrogen, represents in each case optionally substituted alkyl, phenyl or phenylalkyl,
    • R1 represents hydrogen, represents in each case optionally substituted saturated or unsaturated alkyl or cycloalkyl, each of which is optionally interrupted by heteroatoms, represents in each case optionally substituted phenyl or hetaryl, represents in each case optionally substituted phenylalkyl or hetarylalkyl, and
    • R2 represents hydrogen, represents in each case optionally substituted saturated or unsaturated alkyl or alkoxy, represents in each case optionally substituted phenyl, phenylalkyl or phenylalkyloxy, or
    • R1, R2 furthermore together with the nitrogen atom to which they are attached may represent an optionally substituted cycle which is optionally interrupted by one or more heteroatoms.
  • For the compounds of the formula (I)′, the following applies:
    • Ar preferably represents Ar1, where Ar1 represents phenyl, naphthyl or mono- or bicyclic hetaryl having five to ten ring atoms, each of which is optionally mono- to pentasubstituted by halogen, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkinyl, C1-C8-alkoxy, C2-C8-alkenyloxy, C3-C8-alkinyloxy, C1-C8-alkylthio, C1-C6-alkylsulphonyl, C1-C6-halogenoalkyl, C1-C6-halogenoalkoxy, C2-C8-halogenoalkenyloxy, C1-C2-alkylidenediyl-dioxy, C1-C2-halogenoalkylidenediyl-dioxy, halogeno-C1-C4-alkylthio, halogeno-C1-C4-alkylsulphonyl, hydroxyl, mercapto, nitro, cyano, amino or by the groups
      Figure US20060100106A1-20060511-C00019
    •  or represents Ar2, where Ar2 represents Ar1 which is additionally substituted by phenyl, naphthyl, five- or six-membered hetaryl, phenyl-C1-C4-alkyl, phenoxy, phenyl-S(O)g-, five- or six-membered hetaryloxy or hetaryl-S(O)g, where these substituents for their part are each optionally mono- to tetrasubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, nitro or cyano, where g represents 0, 1 or 2.
    • K preferably represents oxygen or sulphur.
    • L preferably represents oxygen or sulphur.
    • X preferably represents
      Figure US20060100106A1-20060511-C00020
    • Y preferably represents hydrogen, C1-C12-alkyl, C3-C10-alkenyl, C1-C6-alkoxy-C2-C4-alkyl, C1-C6-alkylthio-C2-C4-alkyl, C1-C8-halogenoalkyl, represents in each case optionally C1-C6-alkyl-, C1-C6-alkoxy-, C1-C4-halogenoalkyl- or halogen-substituted C3-C8-cycloalkyl or C3-C8-cycloalkyl-C1-C4-alkyl, optionally interrupted in the cycle by oxygen or sulphur, represents phenyl-C1-C4-alkyl or five- or six-membered hetaryl-C1-C4-alkyl, each of which is optionally mono- to tetrasubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, cyano or nitro.
    • Z preferably represents hydrogen, C1-C6-alkyl, represents phenyl or phenyl-C1-C4-alkyl, each of which is optionally mono- to trisubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, nitro or cyano.
    • R1 preferably represents hydrogen, represents in each case optionally fluorine and/or chlorine-substituted C1-C10-alkyl, C3-C10-alkenyl, C3-C6-alkinyl, represents in each case optionally fluorine-, chlorine-, C1-C4-alkyl-, C1-C4-alkoxy-substituted C3-C8-cycloalkyl or C5-C8-cycloalkenyl in which optionally one methylene group may be replaced by oxygen or sulphur, or represents phenyl, pyridyl, thienyl, pyrimidyl, thiazolyl, phenyl-C1-C4-alkyl, pyridyl-C1-C2-alkyl, thiazolyl-C1-C2-alkyl, each of which is optionally mono- to tetrasubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, cyano or nitro.
    • R2 preferably represents hydrogen, C1-C6-alkyl or C3-C6-alkenyl.
    • R1, R2 furthermore together with the nitrogen atom to which they are attached preferably represent an in each case optionally C1-C4-alkyl-substituted five- to eight-membered cycle in which optionally one methylene group may be replaced by oxygen or sulphur.
    • R3 preferably represents in each case optionally fluorine- and/or chlorine-substituted C1-C10-alkyl, C2-C10-alkenyl, C3-C10-alkinyl, C1-C10-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, in each case optionally fluorine, chlorine, C1-C4-alkyl and/or C1-C4-alkoxy-substituted C3-C8-cycloalkyl or C3-C8-cycloalkoxy in which optionally one methylene group may be replaced by oxygen or sulphur, represents phenyl, phenoxy, benzyloxy, five- or six-membered hetaryl or phenyl-C1-C4-alkyl, each of which may optionally be mono- to tetrasubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, cyano or nitro, or, in the case of the radicals a), c) and f) mentioned under Ar, also represents a group
      Figure US20060100106A1-20060511-C00021
    • R4 preferably represents hydrogen or C1-C4-alkyl.
    • R5 preferably represents hydrogen or optionally fluorine- and/or chlorine-substituted C1-C4-alkyl.
    • R6 preferably represents hydrogen, in each case optionally fluorine- and/or chlorine-substituted C1-C10-alkyl, C3-C8-alkenyl, C3-C8-alkinyl, C1-C10-alkoxy, C3-C8-alkenyloxy, optionally fluorine-, chlorine-, C1-C4-alkyl or C1-C4-alkoxy-substituted C3-C8-cycloalkyl in which optionally one methylene group may be replaced by oxygen or sulphur, represents phenyl, phenyl-C1-C4-alkyl or phenyl-C1-C2-alkoxy, each of which is optionally mono- to tetrasubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, cyano or nitro.
    • R7 preferably represents hydrogen, C1-C6-alkyl or C3-C6-alkenyl.
    • R6, R7 furthermore together with the nitrogen atom to which they are attached preferably represent an optionally C1-C4-alkyl-substituted five- to eight-membered cycle in which optionally one methylene group may be replaced by oxygen or sulphur.
  • For the compounds of the formula (I)′, the following applies:
    • K particularly preferably represents oxygen or sulphur.
    • Ar particularly preferably represents Ar1, where Ar1 represents phenyl, naphthyl, quinolinyl, thienyl, pyrimidyl, furanyl, thiazolyl, benzothiazolyl, oxazolyl, pyrazolyl or pyridyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkinyloxy, C1-C6-alkylthio, C1-C4-alkylsulphonyl, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, C2-C4-halogenoalkenyloxy, C1-C2-alkylidenediyl-dioxy, C1-C2-halogenoalkylidenediyl-dioxy, halogeno-C1-C2-alkylthio, halogeno-C1-C2-alkylsulphonyl, hydroxyl, mercapto, nitro, cyano, amino or by one of the following groups
      Figure US20060100106A1-20060511-C00022
    •  or represents Ar2, where Ar2 represents Ar1 which is additionally substituted by phenyl, pyridyl, pyrimidyl, thienyl, furanyl, thiazolyl, tetrazolyl, triazolyl, benzyl, phenoxy, phenyl-S(O)g-, pyridyloxy, pyrimidyloxy, thiazolyloxy, pyridyl-S(O)g-, pyrimidyl-S(O)g- or thiazolyl-S(O)g-, where these substituents for their part are optionally mono- to trisubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C2-C4-alkenyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, nitro or cyano, where g represents 0, 1 or2.
    • X particularly preferably represents
      Figure US20060100106A1-20060511-C00023
    • Y particularly preferably represents hydrogen, C1-C10-alkyl, C1-C6-halogenoalkyl, C3-C8-alkenyl, C1-C4-alkoxy-C2-C3-alkyl, C1-C4-alkylthio-C2-C3-alkyl, represents optionally C1-C4-alkyl-, C1-C4-alkoxy-, C1-C2-halogenoalkyl-, fluorine- or chlorine-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C2-alkyl, represents phenyl-C1-C2-alkyl, thiazolylmethyl or pyridylmethyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, cyano or nitro.
    • Z particularly preferably represents hydrogen, C1-C3-alkyl, represents phenyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, nitro or cyano.
    • R1 particularly preferably represents hydrogen, represents in each case optionally fluorine- and/or chlorine-substituted C1-C6-alkyl, C2-C6-alkenyl, C3-C4-alkinyl, represents optionally fluorine-, chlorine-, C1-C2-alkyl-, C1-C2-alkoxy-substituted C3-C6-cycloalkyl or represents phenyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, cyano or nitro.
    • R2 particularly preferably represents hydrogen, represents in each case optionally fluorine- and/or chlorine-substituted C1-C4-alkyl or C3-C4-alkenyl.
    • R1, R2 furthermore together with the nitrogen atom to which they are attached particularly preferably represent an optionally methyl-substituted five- or six-membered cycle in which optionally one methylene group may be replaced by oxygen.
    • R3 particularly preferably represents in each case optionally fluorine- and/or chlorine-substituted C1-C6-alkyl, C2-C6-alkenyl, C3-C6-alkinyl, C1-C6-alkoxy, C1-C4-alkoxy-C1-C2-alkyl, C1-C4-alkylthio-C1-C2-alkyl, in each case optionally fluorine-, chlorine-, C1-C2-alkyl- and/or C1-C2-alkoxy-substituted C3-C6-cycloalkyl or C3-C6-cycloalkoxy in which optionally one methylene group may be replaced by oxygen, represents phenyl, phenoxy, benzyloxy, thienyl, furanyl, pyridyl, pyrimidyl, thiazolyl, pyrazolyl or phenyl-C1-C2-alkyl, each of which may optionally be mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro, or, in the case of the radicals a), c) and f) mentioned under Ar, also represents a group
      Figure US20060100106A1-20060511-C00024
    • R4 particularly preferably represents hydrogen.
    • R5 particularly preferably represents hydrogen, methyl or ethyl.
    • R6 particularly preferably represents hydrogen, in each case optionally fluorine- and/or chlorine-substituted C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkinyl, C1-C6-alkoxy, C3-C6-cycloalkyl, in which optionally one methylene group may be replaced by oxygen, represents phenyl or phenyl-C1-C2-alkyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro.
    • R7 particularly preferably represents hydrogen or C1-C4-alkyl.
    • R6, R7 furthermore together with the nitrogen atom to which they are attached particularly preferably represent an optionally C1-C2-alkyl-substituted five- or six-membered cycle in which optionally one methylene group may be replaced by oxygen.
  • For the compounds of the formula (I)′, the following applies:
    • K very particularly preferably represents oxygen or sulphur.
    • Ar very particularly preferably represents Ar1, where Ar1 represents phenyl which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, s-, n-, i- or t-butyl, methoxy, ethoxy, propoxy, i-propoxy, s-, n-, i- or t-butoxy, allyloxy, methallyloxy, 2-butenyloxy, propargyloxy, 2-butinyloxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylenedioxy, difluoromethylenedioxy, tetrafluoroethylenedioxy, difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, hydroxyl, mercapto, nitro, cyano or amino, or represents pyridyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, methylthio, ethylthio or trifluoromethyl, or represents Ar2, where Ar2 represents Ar1 which is additionally substituted by phenyl, pyridyl, thienyl, tetrazolyl, triazolyl or phenoxy, where these substituents for their part are optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, s-, n-, i- or t-butyl, methoxy, ethoxy, i-propoxy, s-, n- or t-butoxy, trifluoromethyl, trifluoromethoxy, nitro or cyano.
    • X very particularly preferably represents
      Figure US20060100106A1-20060511-C00025
    • Y very particularly preferably represents hydrogen, C1-C6-alkyl, C1-C4-halogenoalkyl, allyl, 3-butenyl, C1-C4-alkoxy-C2-alkyl, represents in each case optionally methyl-, methoxy-, trifluoromethyl-, fluorine- or chlorine-substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl or represents benzyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methoxy, methyl, trifluoromethyl, trifluoromethoxy, cyano or nitro or represents optionally chlorine-substituted pyridylmethyl or triazolylmethyl.
    • Z very particularly preferably represents hydrogen, methyl, ethyl, represents phenyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro.
    • R3 very particularly preferably represents methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl, vinyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, n-, s-, i- or t-butyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cyclopentyloxy, cyclohexyloxy, represents phenyl, pyridyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, n-, s-, i- or t-butyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro, or, in the case of the radicals a), c) and f) mentioned under Ar, also represents a group
      Figure US20060100106A1-20060511-C00026
    • R5 very particularly preferably represents hydrogen or methyl.
    • R6 very particularly preferably represents hydrogen, methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, represents phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro.
    • R7 very particularly preferably represents hydrogen, methyl or ethyl.
    • R6, R7 together with the nitrogen atom to which they are attached very particularly preferably represent a pyrrolidine, piperidine or morpholine radical.
  • For the compounds of the formula (I)′, the following applies:
    • K especially preferably represents oxygen.
    • Ar especially preferably represents Ar1, where Ar1 represents phenyl which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl, methoxy, ethoxy, propoxy, isopropoxy, n-, s-, i- or t-butoxy, allyloxy, methallyloxy, 2-butenyloxy, propargyloxy, 2-butinyloxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylenedioxy, difluoromethylenedioxy, tetrafluoroethylenedioxy, difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, hydroxyl, nitro, mercapto, cyano or amino or represents pyridyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, propoxy, i-propoxy or trifluoromethyl,
    •  or represents Ar2, where Ar2 represents Ar1 which is additionally substituted by phenyl or phenoxy, where these substituents for their part are optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, n-, s-, i- or t-butyl, methoxy, ethoxy, isopropoxy, n-, s-, i- or t-butoxy, trifluoromethyl, trifluoromethoxy, nitro or cyano.
    • X especially preferably represents CN.
    • Y especially preferably represents hydrogen, C1-C6-alkyl, C1-C3-halogenoalkyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl.
    • Z especially preferably represents hydrogen or methyl.
  • All of the abovementioned compounds of the formula (I) can be present both as cis and as trans isomers. To simplify the presentation, in each case only one isomer is shown in the formulae of the compounds. However, the respective other isomer is likewise included in the invention.
  • The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials and intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, i.e. including combinations between the given preferred ranges.
  • Preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being preferred (preferable).
  • Particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being particularly preferred.
  • Very particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being very particularly preferred.
  • Especial preference according to the invention is given to the compounds of the formula (I) which contain a combination listed above as being especially preferred.
  • Saturated or unsaturated hydrocarbon radicals, such as alkyl or alkenyl, can in each case be straight-chain or branched as far as this is possible, including in combination with heteroatoms, such as, for example, in alkoxy.
  • Unless indicated otherwise, optionally substituted radicals can be mono- or polysubstituted, where in the case of polysubstitution, the substituents can be identical or different.
  • It has been found that the novel compounds of the formula (I) are obtained by the process described below:
  • (A) compounds of the formula (I)
    Figure US20060100106A1-20060511-C00027
    in which
    • Ar, X, Y and Z are each as defined above and
    • K represents oxygen
      • are obtained when
      • compounds of the formula (II)
        Figure US20060100106A1-20060511-C00028
        in which
    • Ar and X are each as defined above,
      • are reacted with compounds of the formula (III)
        Figure US20060100106A1-20060511-C00029
        in which
    • Y and Z are each as defined above but do not represent hydrogen and
    • W represents O or S(O)g, where g represents 0 or 2, and
    • R8 represents alkyl, in particular C1-C6-alkyl, or benzyl, if appropriate in the presence of a diluent and if appropriate in the presence of a base or an acid and/or a metal compound of the formula (IV)
      Me(V)2  (IV)
      in which
    • Me represents a divalent transition metal atom, in particular nickel, and
    • V represents a chelate ligand, in particular a bidentate chelate ligand, such as, for example, acetylacetonate (R. G. Glushkov et al., Khim.-Farm. Zh. 24, (7), (1990), 24-27; M. V. Mezentseva et al., Khim.-Farm. Zh. 25,(12), (1991), 19-23; G. Dannhardt, A. Bauer, Pharmazie 51,(1996), 805-810).
      (B) Moreover, it has been found that compounds of the formula (I)
      Figure US20060100106A1-20060511-C00030
      in which
    • Ar, X, Y and Z are each as defined above and
    • K represents oxygen,
      • are obtained when compounds of the formula (V)
        Figure US20060100106A1-20060511-C00031
        in which
    • Ar and X are each as defined above, and
    • Hal represents halogen, in particular chlorine or bromine, are reacted with compounds of the formula (VI)
      Figure US20060100106A1-20060511-C00032
      in which
    • Y and Z are each as defined above, but do not represent hydrogen,
      • if appropriate in the presence of a diluent, to give compounds of the formula (VII)
        Figure US20060100106A1-20060511-C00033
        in which
    • Ar, X, Y and Z are each as defined above
      • which are reacted further, if appropriate in the presence of a base and if appropriate in the presence of a trivalent phosphorus compound (for example triphenylphosphine, triethyl phosphite), with elimination of sulphur and hydrogen halide, to give compounds of the formula (I)
      • in which
    • Ar, X, Y and Z are each as defined above
      • (see A. Eschenmoser et al., Helv. Chim. Acta 54, (1971), 710-734; V. Issartel et al., C.R. Acad. Sci., Ser. II, Mec., Phys., Chim., Astron. 321, (12), (1995), 521-524).
        (C) Furthermore, it has been found that compounds of the formula (I)
        Figure US20060100106A1-20060511-C00034
        in which
      • Ar, X, Y and Z are each as defined above and K represents oxygen, are obtained when compounds of the formula (II)
        Figure US20060100106A1-20060511-C00035
        in which
      • Ar and X are each as defined above, are initially condensed with compounds of the formula (VIII)
        Figure US20060100106A1-20060511-C00036
        in which
      • Z is as defined above and
      • R9 represents C1-C4-alkyl, preferably methyl and ethyl, and the resulting intermediates are, preferably without intermediate isolation, reacted with amines of the formula (IX)
        Y—NH2  (IX)
        in which
      • Y is as defined above,
      • if appropriate in the presence of a diluent and if appropriate in the presence of a base.
        (D) Furthermore, it has been found that compounds of the formula (I)
        Figure US20060100106A1-20060511-C00037
        in which
      • Ar, X, Y and Z are each as defined above and
      • K represents sulphur,
      • are obtained when compounds of the formula (I)
        Figure US20060100106A1-20060511-C00038
        in which
      • Ar, X, Y and Z are each as defined above and
      • K represents oxygen
      • are reacted in the presence of a sulphurizing agent, such as, for example, phosphorus pentasulphide or 2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiaphosphetane 2,4-disulphide (Lawesson's reagent) in the presence of a solvent.
        (E) Moreover, it has been found that compounds of the formula (I)
        Figure US20060100106A1-20060511-C00039
        in which
      • Ar, X, Y and Z are each as defined above,
      • Ar has the meaning given above for Ar2 and
      • K represents oxygen,
      • are obtained when compounds of the formula (I1)
        Figure US20060100106A1-20060511-C00040
        in which
      • Ar1, X, Y and Z are each as defined above and
      • Hal represents halogen, in particular bromine,
      • are reacted with boronic acids of the formula (X)
        Ar2′—B(OH)2  (X),
        in which
      • Ar2′ represents the substituents which have been mentioned above under Ar2 as additional substituents for Ar1,
      • in the presence of a solvent, if appropriate in the presence of a base and a noble metal complex, preferably a palladium complex.
  • Using, according to process A, for example 4-methyl-benzoylacetonitrile and methyl N-ethyliminoacetate as starting materials, the course of the reaction can be represented by the following reaction scheme:
    Figure US20060100106A1-20060511-C00041
  • Using, according to process B, for example 2-bromo-2-(3-chlorobenzoyl)acetonitrile and N-methylthiobenzamide as starting materials, the course of the reaction can be represented by the following reaction scheme:
    Figure US20060100106A1-20060511-C00042
  • Using, according to process C, for example 3,4-dichloro-benzoyl-acetonitrile, methyl orthoacetate and isopropylamine as starting materials, the course of the reaction can be represented by the following reaction scheme:
    Figure US20060100106A1-20060511-C00043
  • Using, according to process D, for example Z-2-(4-trifluoromethyl-benzoyl)-3-(N-methylamino)crotononitrile and Lawesson's reagent as starting materials, the course of the reaction can be represented by the following reaction scheme:
    Figure US20060100106A1-20060511-C00044
  • Using, according to process E, for example 2-(4-bromo-benzoyl)-3-(N-methylamino)crotononitrile and 4-chloro-phenylboronic acid as starting materials, the course of the reaction can be represented by the following reaction scheme:
    Figure US20060100106A1-20060511-C00045
  • The compounds of the formula (II)
    Figure US20060100106A1-20060511-C00046
    in which
  • Ar, X are each as defined above, required as starting materials in process (A) are known or can be prepared by processes known in principle from the literature (Organikum, 16th revised edition, pp. 415, 417, VEB Deutscher Verlag der Wissenschaften, Berlin 1986, German Patent Applications with the application numbers 198 519 86 and 10 007 286 and WO 00/27 812).
  • The compounds of the formula (II) are obtained, for example, by hydrolysing compounds of the formula (XI)
    Figure US20060100106A1-20060511-C00047
    in which
      • Ar is as defined above,
        • R10 represents alkyl, in particular C1-C6-alkyl, or benzyl, which may optionally be substituted,
          in the presence of an acid (for example an inorganic acid, such as hydrochloric acid) or a base (for example an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide) and if appropriate in the presence of a diluent (for example an aqueous alcohol, such as methanol or ethanol), at temperatures between 0° C. and 200° C., preferably between 20° C. and 150° C., followed by decarboxylation, where the elimination of the radical may optionally also be carried out hydrolytically by known processes (Bowman, Fordham, J. Chem. Soc. 1951, 2758) using molecular hydrogen at pressures between 1 and 100 bar, if appropriate in the presence of a solvent, such as, for example, methanol, ethanol or ethyl acetate, at temperatures between −20 and 100° C., preferably at room temperature, in the presence of a transition metal, such as, for example, palladium, nickel, rhodium or platinum, which is optionally immobilized on a support, such as, for example, activated carbon or barium sulphate.
  • The compounds of the formula (XI) can be prepared by known processes (Organikum, 16th revised edition, p. 480, VEB Deutscher Verlag der Wissenschaften, Berlin 1986).
  • The compounds of the formula (XI) are obtained, for example, by reacting compounds of the formula (XII)
    Figure US20060100106A1-20060511-C00048
    in which
    • Ar is as defined above,
      • with cyanoacetic acid esters of the formula (XIII)
        Figure US20060100106A1-20060511-C00049
        in which
      • R10 represents alkyl, in particular C1-C6-alkyl, or benzyl,
  • in the presence of a base (for example a metal alkoxide, such as sodium methoxide or sodium ethoxide) and if appropriate in the presence of a diluent (for example ether or the alcohol which is derived from the alkoxide), at temperatures of from 0° C. to 150° C., preferably between 20 and 120° C.
  • Some of the compounds of the formula (XII) are novel, and they can be prepared by processes known in principle (for example Organikum, 16th revised edition, p. 423, VEB Deutscher Verlag der Wissenschaften, Berlin 1986).
  • The compounds of the formula (XII) are obtained, for example, by reacting compounds of the formula (XIV)
    Figure US20060100106A1-20060511-C00050
    in which
    • Ar is as defined above,
  • with halogenating agents (for example thionyl chloride, phosgene, phosphorus trichloride), if appropriate in the presence of a diluent (for example optionally chlorinated aliphatic or aromatic hydrocarbons, such as toluene or methylene chloride), at temperatures of from 0° C. to 150° C., preferably between 20° C. and 100° C.
  • Cyanoacetic acid esters of the formula (XIII) are known compounds of organic chemistry.
  • Some of the compounds of the general formula (XIV-b)
    Figure US20060100106A1-20060511-C00051
    in which
    • B1 represents hydrogen or fluorine and
    • B8 represents hydrogen, hydroxyl, represents in each case optionally cyano-, halogen-, alkoxy-, alkylcarbonyl- or alkoxycarbonyl-substituted alkyl, alkyl-carbonyl, alkoxycarbonyl, alkylthio or alkylsulphonyl, represents in each case optionally halogen-substituted alkenyl or alkinyl, represents in each case optionally halogen- or alkyl-substituted cycloalkyl or cycloalkylalkyl, represents in each case optionally halogen-substituted alkoxy or alkenyloxy, represents in each case optionally cyano-, halogen-, alkyl-, halogenoalkyl-, alkoxy- or halogenoalkoxy-substituted arylalkyl or arylalkoxy,
      are known, or they can be synthesized by known processes.
  • Here, B8 preferably represents hydrogen, hydroxyl, represents in each case optionally cyano-, halogen-, C1-C4-alkoxy-, C1-C4-alkylcarbonyl- or C1-C4-alkoxycarbonyl-substituted C1-C8-alkyl, C1-C8-alkylcarbonyl, C1-C8-alkoxycarbonyl, C1-C8-alkylthio or C1-C8-alkylsulphonyl, represents in each case optionally halogen-substituted C2-C6-alkenyl or C2-C6-alkinyl, represents in each case optionally halogen- or C1-C4-alkyl-substituted C3-C8-cycloalkyl or C3-C8-cycloalkyl-C1-C4-alkyl, represents in each case optionally halogen-substituted C1-C8-alkoxy or C2-C8-alkenyloxy, represents in each case optionally cyano-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkoxy-substituted phenyl-C1-C4-alkyl or penyl-C1-C4-alkoxy.
  • The novel compounds are obtained, inter alia, by converting compounds of the general formula (XV)
    Figure US20060100106A1-20060511-C00052
    in which
  • B1 represents hydrogen or fluorine and
  • B8is as defined above,
  • by processes known per se using CO2 in the presence of organometallic compounds into compounds of the general formula (XIV-b) (for example Organikum, 16th revised edition, p. 499, VEB Deutscher Verlag der Wissenschaften 1986).
  • Suitable for use as organometallic bases are, in addition to organomagnesium compounds, also organolithium compounds, which are known chemicals for synthesis of organic chemistry. Suitable solvents/diluents are hydrocarbons (such as toluene) or ethers (such as, for example, tetrahydrofuran or diethyl ether). It is also possible to use mixtures of the abovementioned solvents.
  • The reaction temperature is usually between −100° C. and 80° C., preferably between −80° C. and 25° C. (room temperature). For work-up, the reaction mixture is diluted with water or an inorganic acid, such as, for example, hydrochloric acid, which may be diluted or concentrated, and the product is isolated using a water-immiscible solvent and purified by customary methods, for example by crystallization.
  • Some of the compounds of the general formula (XV) in which
  • B1 represents hydrogen or fluorine and
  • B8 is as defined above,
  • are novel, and they can be synthesized by known processes (Sicker et al., Tetrahedron, 31, (1996), 10389; Bell et al., J. Med. Chem., 33, (1990), 380).
  • The novel compounds of the formula (XV) in which
      • B1 represents hydrogen or fluorine and
      • B8 represents in each case optionally cyano-, halogen-, alkoxy-, alkylcarbonyl- or alkoxycarbonyl-substituted alkyl, alkylcarbonyl, alkoxycarbonyl, alkylthio or alkylsulphonyl, represents in each case optionally halogen-substituted alkenyl or alkinyl, represents in each case optionally halogen- or alkyl-substituted cycloalkyl or cycloalkylalkyl, represents in each case optionally cyano-, halogen-, alkyl-, halogenoalkyl-, alkoxy- or halogenoalkoxy-substituted arylalkyl,
        are obtained, inter alia, from compounds of the general formula (XV)′
        Figure US20060100106A1-20060511-C00053
        in which B1 represents hydrogen or fluorine and B9 represents hydrogen, by reaction with an alkylating agent of the formula (XVI)
        B8—X1   (XVI),
        in which
      • B8 represents in each case optionally cyano-, halogen-, alkoxy-, alkylcarbonyl- or alkoxycarbonyl-substituted alkyl, alkylcarbonyl, alkoxycarbonyl, alkylthio or alkylsulphonyl, represents in each case optionally halogen-substituted alkenyl or alkinyl, represents in each case optionally halogen- or alkyl-substituted cycloalkyl or cycloalkylalkyl, represents in each case optionally cyano-, halogen-, alkyl-, halogenoalkyl-, alkoxy- or halogenoalkoxy-substituted arylalkyl and
      • X1 represents halogen, in particular iodine, bromine or chlorine, or other leaving groups, for example activated esters, such as mesylate or tosylate, or
  • from compounds of the general formula (XV)′ in which B1 represents hydrogen or fluorine and B9 represents hydroxyl, by reaction with an alkylating agent of the formula (XVII)′
    B10—X1   (XVII)′,
    in which
      • B10 represents in each case optionally halogen-substituted alkyl or alkenyl or represents in each case optionally cyano-, halogen-, alkyl-, halogenoalkyl-, alkoxy- or halogenoalkoxy-substituted arylalkyl and
      • X1 represents halogen, in particular iodine, bromine or chlorine, or other leaving groups, for example activated esters, such as mesylate or tosylate,
        if appropriate in the presence of a base and in the presence of a solvent.
  • Bases suitable for use in the reaction are, in addition to alkali metal oxides and alkaline earth metal oxides, tertiary amines, such as triethylamine, pyridine or N,N-diethylaniline, which may be used in molar ratios or else in excess.
  • Suitable solvents or diluents are, in addition to hydrocarbons such as toluene, also halogenated hydrocarbons, such as dichloromethane. It is possible to use polar aprotic solvents/diluents, such as dimethylformamide, and also mixtures of the abovementioned solvents. The reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably between −10° C. and 80° C.
  • The compounds of the general formula (XV)′, in which B1 represents hydrogen or fluorine and B9 represents hydrogen are known from the literature (Huang et al., Synthesis (1984), 851; JP 63132881) and can be converted by oxidation according to processes known per se into compounds of the general formula (XV)′ in which B1 represents hydrogen or fluorine and B9 represents hydroxyl (P. G. Sammes et al., J. Chem. Soc., Perkin Trans I, (1979), 2481).
  • Furthermore, compounds of the general formula (XIV-b) in which
  • B1 represents hydrogen or fluorine and
  • B8 is as defined above,
    can be obtained by hydrolysing compounds of the formula (XVIII)
    Figure US20060100106A1-20060511-C00054
    in which
      • B1 represents hydrogen or fluorine,
      • B8 is as defined above and
      • B11 represents alkyl or benzyl, in particular C1-C6-alkyl or benzyl, which may optionally be fully or partially substituted by the radicals R1 or R2,
        in the presence of an acid (for example an inorganic acid, such as hydrochloric acid) or a base (for example an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide) and if appropriate in the presence of a diluent (for example an aqueous alcohol, such as methanol or ethanol), at temperatures between 0° C. and 200° C., preferably between 20° C. and 150° C. The radical B11 can optionally also be removed hydrogenolytically using molecular hydrogen at pressures between 1 and 100 bar, if appropriate in the presence of a solvent, for example methanol, ethanol or ethyl acetate, at temperatures between −10° C. and 100° C., preferably at room temperature, in the presence of a transition metal, for example palladium, nickel, rhodium or platinum, which may optionally be immobilized on a support, such as activated carbon or barium sulphate, using known processes (Bowman, Fordham J. Chem. Soc., 1951, 2758).
  • Furthermore, compounds of the general formula (XVIII) in which
      • B1 represents hydrogen or fluorine and
      • B8 is as defined above and
      • B11 represents hydrogen, alkyl or benzyl, in particular C1-C6-alkyl or benzyl, which may optionally in each case be fully or partially substituted by the radicals R1 or R2,
        can be obtained according to customary processes known per se, by reacting compounds of the general formula (XV) in which
      • B1 represents hydrogen or fluorine and
      • B8 is as defined above,
        with a nucleophile of the general formula (XIX)
        Figure US20060100106A1-20060511-C00055
        in which
      • B11 represents hydrogen, alkyl or benzyl, in particular C1-C6-alkyl or benzyl, which may optionally in each case be fully or partially substituted by the radicals R1 or R2,
        in the presence of CO at pressures of from 1 bar to 100 bar, preferably between 1 bar and 50 bar, and at temperatures between 20° C. and 300° C., preferably between 20° C. and 150° C., in the presence of a catalyst, for example palladium salts or cobalt salts or transition metal carbonyl compounds, such as, for example, Co2(CO)8, if appropriate in the presence of a ligand (such as, for example, triphenylphosphine, trisodium (3-sulphonylphenyl)phosphine, in the presence of a base (for example an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, or else organic bases, such as triethylamine or pyridine) and of a diluent (for example alcohols, water, tetrahydrofuran, dichloromethane, toluene or mixtures of the abovementioned diluents). The reaction can optionally also be carried out in the presence of phase-transfer catalysts (for example glycols, crown ethers or ammonium salts, such as tetrabutylammonium bromide or chloride) or auxiliaries (for example zeolites) or under irradiation with light, according to known processes (Ziolkowski et al., J. Mol. Catal. A: Chem., 154, (2000), 93; P. Kalck et al., J. Organomet. Chem., 482, (1994), 45; Du Pont de Nemours & Co U.S. Pat. No. 2,734,912; Alper, H. et al., Angew. Chem., 96, (1984), 710; Takatori K. et al., Tetrahedron, 54, (1998), 15861).
  • Furthermore, compounds of the general formula (XIV-b)
    Figure US20060100106A1-20060511-C00056
    in which
      • B1 represents hydrogen or fluorine and
      • B8 represents in each case optionally cyano-, halogen-, alkoxy-, alkylcarbonyl- or alkoxycarbonyl-substituted alkyl, alkylcarbonyl, alkoxycarbonyl, alkylthio or alkylsulphonyl, represents in each case optionally halogen-substituted alkenyl or alkinyl, represents in each case optionally halogen- or alkyl-substituted cycloalkyl or cycloalkylalkyl, represents in each case optionally cyano-, halogen-, alkyl-, halogenoalkyl-, alkoxy- or halogenoalkoxy-substituted arylalkyl,
        can be obtained from compounds of the general formula (XIV-b),
        in which
      • B1 represents hydrogen or fluorine and
      • B8 represents hydrogen,
        by reaction with an alkylating agent of the formula (XVII)′
        B10—X1  (XVII)′
        in which
      • B10 represents in each case optionally halogen-substituted alkyl or alkenyl or represents in each case optionally cyano-, halogen-, alkyl-, halogenoalkyl-, alkoxy- or halogenoalkoxy-substituted arylalkyl and
      • X1 represents halogen, in particular iodine, bromine or chlorine, or other leaving groups, for example activated esters, such as mesylate or tosylate,
        if appropriate in the presence of a base and in the presence of a solvent.
  • Bases suitable for use in the reaction are, in addition to alkali metal oxides and alkaline earth metal oxides, tertiary amines such as triethylamine, pyridine or N,N-diethylaniline, which can be used in molar ratios or else in excess. Suitable solvents are, in addition to hydrocarbons such as toluene, also halogenated hydrocarbons, such as dichloromethane. It is possible to use polar aprotic solvents/diluents, such as dimethylformamide, and also mixtures of the abovementioned solvents. The reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably between −10° C. and 80° C.
  • Some of the compounds of the formula (III)
    Figure US20060100106A1-20060511-C00057
    in which
  • W, Y, Z and R8 are each as defined above,
  • likewise required as starting materials are known, and they can be prepared by known processes (see Example III-a-1 and H. Bredereck, F. Effenberger, E. Henseleit, Chem. Ber. 1965, 98, 2754; P. Deslongchamps, O. C. Ukken, A. Guida, R. J. Taillefer,
  • Nouv. J. Chim. 1977, 235, 240; R. M. Moriarty, C. L. Yeh, K. C. Ramey, P. W. Whiteburst, J. Am. Chem. Soc. 1970, 21, 6360).
  • Some of the compounds of the formula (V)
    Figure US20060100106A1-20060511-C00058
    in which
  • Ar and Hal are each as defined above and X represents cyano,
  • are known, or they can be prepared by known processes (Gakhar H. K. et. al, J. Indian Chem. Soc. 43 (1971) 953; Corsaro A. Heterocycles 23 (1985) 2645).
  • The compounds of the formula (VI)
    Figure US20060100106A1-20060511-C00059
    in which
  • Z and Y are each as defined above,
  • are compounds of organic chemistry which are known in principle, and some are commercially available (see also Preparation Example 5).
  • The compounds of the formula (VIII)
    Figure US20060100106A1-20060511-C00060
    in which
  • Z and R9 are each as defined above,
  • are compounds of organic chemistry which are known in principle, and some of them are commercially available.
  • Most of the compounds of the formula (IX) are commercially available compounds, or they can be prepared by generally known processes of organic chemistry.
  • Some of the arylboronic acids of the formula (X) required for carrying out process E are commercially available, or they can be prepared by known processes.
  • Suitable diluents for process (A) are all organic solvents which are inert towards the reactants. Preference is given to using optionally chlorinated aliphatic or aromatic hydrocarbons, such as toluene, xylene, mesitylene, chlorobenzene, chloroform, methylene chloride, furthermore polar solvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide, dimethylacetamide or N-methylpyrrolidone. It is also possible to use ethers, such as diethyl ether, tetrahydrofuran or dioxane.
  • Bases suitable for use in process (A) are all customary acid acceptors which do not hydrolyse the reactants.
  • Preference is given to use tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN) or N,N-dimethylaniline.
  • Acids suitable for use in process (A) are all acids which do not hydrolyse the reactants. Preference is given to using organic acids, such as p-toluenesulphonic acid and trifluoroacetic acid.
  • When carrying out process (A), the reaction temperatures can be varied within a relatively wide range. The process is expediently carried out at temperatures between −20° C. and 160° C., preferably between 0° C. and 120° C.
  • The process (A) is preferably carried out under atmospheric pressure.
  • When carrying out process (A), the reaction component of formula (III) is employed in equimolar amounts or in a relatively large excess (up to 5 mol), preferably in 1.5 to 2 times the molar amount, based on the reaction component of the formula (II).
  • The base which is optionally employed is preferably used in an amount which is equimolar to that of the reaction component of the formula (II). The acid that is employed, if appropriate, is preferably used in catalytic amounts.
  • The process (B) is characterized in that compounds of the formula (V) are in each case reacted with thioamides of the formula (VI), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • The starting materials of the formula (V) can be prepared by known processes (Gakhar H. K. et al., J. Indian Chem. Soc. 43, (1971), 953 or Corsaro A., Heterocycles 23, (1985), 2645). The compounds of the formula (VI) can be prepared from the corresponding keto compound using thionylating agents, in particular Lawesson's reagent, in inert solvents, such as, for example, toluene (see Preparation Example 5).
  • Diluents suitable for use in the process (B) according to the invention are all solvents which are inert towards the compounds of the formula (V). Preference is given to using hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin, furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as dimethylformamide, N-methylpyrrolidone, dimethyl sulphoxide and sulpholane.
  • Suitable acid binders for the reaction according to process (B) according to the invention are all customary acid acceptors. Preference is given to using tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base and N,N-dimethylaniline, polymeric bases, such as diisopropylaminopolystyrene, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal carbonates and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.
  • Phosphorus reagents suitable for use in the process (B) according to the invention are alkyl phosphites, such as triethyl phosphite, tributyl phosphite, or triphenylphosphines, such as triphenylphosphine.
  • The reaction temperature in the process (B) according to the invention can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0° C. and 200° C., preferably between +20° C. and 150° C.
  • When carrying out the process (B) according to the invention, the starting materials of the formula (V) and the thioamide of the formula (VI) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess of one component or the other. Work-up is carried out by customary methods.
  • The process (C) is characterized in that initially compounds of the formula (II) are condensed with orthoesters of the formula (VIII), and the resulting condensates are, without intermediate characterization, reacted with amines of the formula (IX).
  • Acid binders suitable for the reaction according to the process (C) according to the invention are, if appropriate, all customary acid acceptors. Preference is given to using tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base and N,N-dimethylaniline, polymeric bases, such as, for example, disopropylaminopolystyrene, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal carbonates and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.
  • Diluents suitable for the process (C) according to the invention are all solvents which are inert towards the orthoesters. Preference is given to using hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin, furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic acid esters, such as ethyl acetate, moreover nitriles such as acetonitrile, and also strongly polar solvents, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulphoxide and sulpholane. According to a further process variant, the orthoesters themselves may also be used as solvents. This process variant is emphasized as being preferred.
  • The reaction temperature in the process (C) according to the invention can be varied within a relatively wide range. In general, the process is carried out at temperatures between −20° C. and 200° C., preferably between 0° C. and 150° C.
  • The process (C) according to the invention is generally carried out under atmospheric pressure.
  • When carrying out the process (C) according to the invention, the starting materials of the formula (II) and the appropriate amine of the formula (IX) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 10 mol, preferably up to 3 mol) of one component or the other. The orthoesters of the formula (VIII) are generally employed in a relatively large excess. Work-up is carried out according to customary methods by concentrating the reaction mixture by removing the diluent and excess reactants under reduced pressure and purifying the residue further.
  • The process (D) is characterized in that compounds of the formula (I) in which Ar, X, Y and Z are each as defined above and K represents oxygen are reacted with sulphurizing agents, if appropriate in the presence of a diluent.
  • The sulphurizing agents to be used are known chemicals for synthesis, such as, for example, phosphorus pentasulphide or 2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiaphosphetane 2,4-disulphide (Lawesson's reagent).
  • Diluents suitable for use in the process (D) according to the invention are all solvents which are inert towards the abovementioned reagents. Preference is given to using hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin, furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, chlorobenzene and o-dichlorobenzene, ethers, such as tetrahydrofuran, dioxane, diisopropyl ether or methyl tert-butyl ether.
  • In the process (D) according to the invention, the reaction temperatures can be varied within a relatively wide range.
  • In general, the process is carried out at temperatures between 0° C. and 250° C., preferably between 40° C. and 200° C.
  • When carrying out the process (D) according to the invention, the starting materials of the formula (I) and the abovementioned reagents are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess of up to 5 mol of the abovementioned reagents. Work-up is carried out by customary methods.
  • Some of the arylboronic acids required for carrying out the process (E), such as, for example, 4-chloro-phenylboronic acid, are commercially available, or they can be prepared by known processes.
  • Suitable acid acceptors for carrying out the process (E) according to the invention are inorganic or organic bases. These preferably include alkaline earth metal hydroxides, acetates, carbonates or bicarbonates or alkali metal hydroxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydroxide, potassium hydroxide, barium hydroxide or ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate or ammonium acetate, sodium carbonate, potassium carbonate or ammonium carbonate, sodium bicarbonate or potassium bicarbonate, alkali metal fluorides, such as, for example, caesium fluoride, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN).
  • Suitable diluents for carrying out the process (E) according to the invention are water, organic solvents and any mixtures thereof. Examples which may be mentioned are: aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane or tetrachloroethylene; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetra-hydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether or anisole; alcohols, such as methanol, ethanol, n- or i-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, di-ethylene glycol monomethyl ether, diethylene glycol monoethyl ether; water.
  • The reaction temperature in the process (E) according to the invention can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0° C. and +200° C., preferably between 50° C. and +150° C.
  • When carrying out the process (E) according to the invention, the boronic acid of the formula (X) in which Ar2′ is as defined above and compounds of the formula (I1) in which Ar1, K, X, Y, Z and Hal are each as defined above are employed in a molar ratio of from 1:1 to 3:1, preferably from 1:1 to 2:1. The catalyst is generally employed in amounts of from 0.005 to 0.5 mol, preferably from 0.01 to 0.1 mol, per mole of the compound of the formula (II). The base is generally employed in excess.
  • The active compounds according to the invention are particularly suitable for use as defoliants, desiccants, haulm-killers and, especially, as weed-killers. By weeds, in the broadest sense, are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
  • The dosages of the active compounds according to the invention required for weed control are between 0.001 and 10 kg/ha, preferably between 0.005 and 5 kg/ha.
  • The active compounds according to the invention can be used, for example, in connection with the following plants:
  • Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
  • Dicotyledonous crops of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.
  • Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
  • Monocotyledonous crops of the genera: Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.
  • According to the invention, it is possible to treat all plants and parts of plants. By plants are to be understood here all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including plant cultivars which can or cannot be protected by plant breeders' certificates. Parts of plants are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubers and rhizomes. Parts of plants also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.
  • The treatment of the plants and parts of plants according to the invention with the active compounds is carried out directly or by action on their environment, habitat or storage area according to customary treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, brushing-on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multi-layer coating.
  • However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants. With respect to the use of the active compounds according to the invention, particular emphasis is given to the use in connection with transgenic plants since in this case synergistically enhanced activities may be observed.
  • The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial cultures, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture-land, and for the selective control of weeds in annual crops.
  • The active compounds according to the invention are highly suitable for the selective control of monocotyledonous weeds in dicotyledonous crops by the pre- and post-emergence method. They can be used very successfully, for example, for the control of harmful grasses in cotton or sugar beet.
  • The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound and very fine capsules in polymeric substances.
  • These formulations are prepared in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, if appropriate with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
  • If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, mineral or vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
  • Suitable solid carriers are:
  • for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
  • Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.
  • It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • The formulations in general contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%, and in addition preferably extenders and/or surfactants.
  • The active compound according to the invention can be present in its commercially available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms, inter alia. In preferred embodiments of the present invention, it is also possible to mix safeners with the compounds according to the invention, to increase crop plant compatibility.
  • Examples of particularly advantageous mixing components are the following:
  • Fungicides:
    • aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
    • benalaxyl, benodanil, benomyl, benzamacril, benzamacryl-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
    • calcium polysulphide, capsimycin, captafol, captan, carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,
    • debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon,
    • edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,
    • famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide, fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,
    • guazatine,
    • hexachlorobenzene, hexaconazole, hymexazole,
    • imazalil, imibenconazole, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP), iprodione, irumamycin, isoprothiolane, isovaledione,
    • kasugamycin, kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture,
    • mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,
    • nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,
    • ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin,
    • paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine-sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,
    • quinconazole, quintozene (PCNB),
    • sulphur and sulphur preparations,
    • tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
    • uniconazole,
    • validamycin A, vinclozolin, viniconazole,
    • zarilamide, zineb, ziram and also
    • Dagger G,
    • OK-8705,
    • OK-8801,
    • α-(1,1 -dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,
    • α-(2,4-dichlorophenyl)-β-fluoro-propyl-1H-1,2,4-triazole-1-ethanol,
    • α-(2,4-dichlorophenyl)-β-methoxy-methyl-1H-1,2,4-triazole-1-ethanol,
    • α-(5-methyl-1,3 -dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,
    • (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,
    • (E)-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,
    • 1-isopropyl {2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,
    • 1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone O-(phenylmethyl)-oxime,
    • 1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,
    • 1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,
    • 1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,
    • 1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,
    • 1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,
    • 1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,
    • 1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,
    • 2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,
    • 2,2-dichloro-N-[1 -(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,
    • 2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,
    • 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,
    • 2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,
    • 2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,
    • 2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,
    • 2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,
    • 2-aminobutane,
    • 2-bromo-2-(bromomethyl)-pentanedinitrile,
    • 2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,
    • 2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,
    • 2-phenylphenol (OPP),
    • 3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,
    • 3,5-dichloro-N-[cyano[(1-methyl-2-propinyl)-oxy]-methyl]-benzamide,
    • 3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
    • 3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,
    • 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)- 1 H-imidazole-1-sulphonamide,
    • 4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,
    • 8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,
    • 8-hydroxyquinoline sulphate,
    • 9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,
    • bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,
    • cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,
    • cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,
    • ethyl [(4-chlorophenyl)-azo]-cyanoacetate,
    • potassium hydrogencarbonate,
    • methanetetrathiol sodium salt,
    • methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,
    • methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,
    • methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,
    • N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,
    • N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,
    • N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,
    • N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,
    • N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,
    • N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,
    • N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,
    • N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide,
    • N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,
    • N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,
    • N-formyl-N-hydroxy-DL-alanine sodium salt,
    • O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,
    • O-methyl S-phenyl phenylpropylphosphoramidothioate,
    • S-methyl 1,2,3-benzothiadiazole-7-carbothioate,
    • spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran]-3′-one,
      Bactericides:
    • bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
      Insecticides/Acaricides/Nematicides:
    • abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,
    • Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin, biopermethrin, BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben,
    • cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin, cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
    • deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoat, dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn,
    • eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp., esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole, etrimfos,
    • fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinam, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox, furathiocarb,
    • granulosis viruses,
    • halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene,
    • imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,
    • lambda-cyhalothrin, lufenuron,
    • malathion, mecarbam, metaldehyde, methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, methidathion, methiocarb, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, monocrotophos,
    • naled, nitenpyram, nithiazine, novaluron, nuclear polyhedrosis viruses,
    • omethoat, oxamyl, oxydemethon M,
    • Paecilomyces fumosoroseus, parathion A, parathion M, permethrin, phenthoat, phorat, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb, propoxur, prothiofos, prothoat, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen, pyriproxyfen,
    • quinalphos,
    • ribavirin,
    • salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos,
    • tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, theta-cypermethrin, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,
    • vamidothion, vaniliprole, Verticillium lecanii,
    • YI 5302,
    • zeta-cypermethrin, zolaprofos,
    • (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl 3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,
    • (3-phenoxyphenyl)-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate,
    • 1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,
    • 2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,
    • 2-(acetlyoxy)-3-dodecyl-1,4-naphthalenedione,
    • 2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,
    • 2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,
    • 3-methylphenyl propylcarbamate
    • 4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,
    • 4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,
    • 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyI)methoxy]-3(2H)-pyridazinone,
    • 4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,
    • Bacillus thuringiensis strain EG-2348,
    • [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,
    • 2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl butanoate,
    • [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,
    • dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,
    • ethyl [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,
    • N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,
    • N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,
    • N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,
    • N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,
    • N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,
    • O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.
      Herbicides:
    • acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, benzobicyclon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinidon(-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop(-P-ethyl), fentrazamide, flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, florasulam, fluazifop(-P-butyl), fluazolate, flucarbazone, flufenacet, flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomesafen, glufosinate-(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop-(-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron(-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
  • Furthermore, the active compound according to the invention, in its commercial formulations and in the use forms prepared from these formulations, can be present as a mixture with synergists. Synergists are compounds which increase the activity of the active compounds without it being necessary for the added synergist to be active itself.
  • The active compound content of the use forms prepared from the commercial formulations can vary within wide ranges. The concentration of active compound in the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
  • Application is carried out in a customary manner adapted to the use forms.
  • The active compounds are furthermore suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene sector. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
  • From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber.
  • From the order of the Diplopoda, for example, Blaniulus guttulatus.
  • From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.
  • From the order of the Symphyla, for example, Scutigerella immaculata.
  • From the order of the Thysanura, for example, Lepisma saccharina.
  • From the order of the Collembola, for example, Onychiurus armatus.
  • From the order of the Blattaria or Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.
  • From the order of the Dermaptera, for example, Forficula auricularia.
  • From the order of the Isoptera, for example, Reticulitermes spp.
  • From the order of the Anoplura, for example, Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.
  • From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp.
  • From the order of the Thysanoptera, for example, Frankliniella occidentalis, Hercinothrips femoralis, Thrips palmi and Thrips tabaci.
  • From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.
  • From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vasturix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.
  • From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris 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, Cnaphalocerus spp. and Aulema oryzae.
  • From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica and Lissorhoptus oryzophilus.
  • From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.
  • From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Liriomyza spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemnia spp. and Liviomyza spp.
  • From the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp.
  • From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans.
  • From the order of the Acarina, for example, Acarus siro, Argas spp., Omithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp. and Brevipulpus spp.
  • The phytoparasitic nematodes include, for example, Pratylenchus spp. Radopholus similis, Ditylenchus dipsaci, Tylenchulus semi penetrans, Heteroderma spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchus spp.
  • The active compounds according to the invention have high insecticidal and acaricidal activity after foliar and soil application.
  • At certain concentrations or application rates, the compounds according to the invention also have fungicidal action. Furthermore, they can also be used as microbicides or antimycotics.
  • When used against hygiene pests and pests of stored products, the active compound has excellent residual activity on wood and clay, and good stability to alkali on limed substrates.
  • The active compounds according to the invention 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, leaf mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas. These parasites include:
  • From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.
  • From the order of the Mallophagida and the suborders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Wemeckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.
  • From the order of the Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.
  • From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.
  • From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
  • From the order of the Blattarida, for example Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.
  • From the subclass of the Acaria (Acarida) and the orders of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Stemostoma spp. and Varroa spp.
  • From the order of the Actinedida (Prostigmata) und Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
  • The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which infest agricultural productive livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese and bees, other pets, such as, for example, dogs, cats, caged birds and aquarium fish, and also so-called test animals, such as, for example, hamsters, guinea pigs, rats and mice. By controlling these arthropods, cases of death and reduction in productivity (for meat, milk, wool, hides, eggs, honey etc.) should be diminished, so that more economic and easier animal husbandry is possible by use of the active compounds according to the invention.
  • 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, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, such as, for example, by injection (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal administration, by dermal use in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of molded articles containing the active compound, such as collars, ear marks, tail marks, limb bands, halters, marking devices and the like.
  • When used for cattle, poultry, pets and the like, the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, free-flowing compositions), which comprise the active compounds in an amount of 1 to 80% by weight, directly or after 100- to 10 000-fold dilution, or they can be used as a chemical bath.
  • It has furthermore been found that the compounds of the formula (I) according to the invention also have a strong insecticidal action against insects which destroy industrial materials.
  • The following insects may be mentioned as examples and as preferred - but without a limitation:
  • Beetles, such as
  • Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderus minutus.
  • Hymenopterons, such as
  • Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur.
  • Termites, such as
  • Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus.
  • Bristletails, such as
  • Lepisma saccarina.
  • Industrial materials in the present connection are to be understood as meaning non-living materials, such as, preferably, plastics, adhesives, sizes, papers and cardboards, leather, wood and processed wood products and coating compositions.
  • Wood and processed wood products are materials to be protected, especially preferably, from insect infestation.
  • Wood and processed wood products which can be protected by the agents according to the invention or mixtures comprising these are to be understood as meaning, for example: building timber, wooden beams, railway sleepers, bridge components, boat jetties, wooden vehicles, boxes, pallets, containers, telegraph poles, wood panelling, wooden windows and doors, plywood, chipboard, joinery or wooden products which are used quite generally in house-building or in building joinery.
  • The active compounds can be used as such, in the form of concentrates or in 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 compounds with at least one solvent or diluent, emulsifier, dispersing agent and/or binder or fixing agent, a water repellent, if appropriate siccatives and UV stabilizers and if appropriate dyestuffs and pigments, and also other processing auxiliaries.
  • The insecticidal compositions or concentrates used for the protection of wood and timber products comprise the active compound according to the invention in a concentration of 0.0001 to 95%-by weight, in particular 0.001 to 60% by weight.
  • The amount of the compositions or concentrates employed depends on the nature and occurrence of the insects and on the medium. The optimum amount employed can be determined for the use in each case by a series of tests. In general, however, it is sufficient to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
  • Solvents and/or diluents which are used are an organochemical solvent or solvent mixture and/or an oily or oil-like organochemical solvent or solvent mixture of low volatility and/or a polar organochemical solvent or solvent mixture and/or water, and if appropriate an emulsifier and/or wetting agent.
  • Organochemical solvents which are preferably used are oily or oil-like solvents having an evaporation number above 35 and a flashpoint above 30° C., preferably above 45° C. Substances which are used as such oily or oil-like water-insoluble solvents of low volatility are appropriate mineral oils or aromatic fractions thereof, or solvent mixtures containing mineral oils, preferably white spirit, petroleum and/or alkylbenzene.
  • Mineral oils having a boiling range from 170 to 220° C., white spirit having a boiling range from 170 to 220° C., spindle oil having a boiling range from 250 to 350° C., petroleum and aromatics having a boiling range from 160 to 280° C., turpentine oil and the like, are advantageously employed.
  • In a preferred embodiment, liquid aliphatic hydrocarbons having a boiling range from 180 to 210° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons having a boiling range from 180 to 220° C. and/or spindle oil and/or monochloronaphthalene, preferably α-monochloronaphthalene, are used.
  • The organic oily or oil-like solvents of low volatility which have an evaporation number above 35 and a flashpoint above 30° C., preferably above 45° C., can be replaced in part by organochemical solvents of high or medium volatility, providing that the solvent mixture likewise has an evaporation number above 35 and a flashpoint above 30° C., preferably above 45° C., and that the insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture.
  • According to a preferred embodiment, some of the organochemical solvent or solvent mixture is replaced by an aliphatic polar organochemical 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.
  • Organochemical binders which are used in the context of the present invention are the synthetic resins and/or binding drying oils which are known per se, are water-dilutable and/or are soluble or dispersible or emulsifiable in the organochemical solvents employed, in particular binders consisting of or comprising an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin, such as indene-cumarone resin, silicone resin, drying vegetable oils and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.
  • The synthetic resin used as the binder can be employed in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances can also be used as binders in an amount of up to 10% by weight. Dyestuffs, pigments, water-repelling agents, odour correctants and inhibitors or anticorrosive agents and the like which are known per se can additionally be employed.
  • It is preferred according to the invention for the composition or concentrate to comprise, as the organochemical binder, at least one alkyd resin or modified alkyd resin and/or one drying vegetable oil. Alkyd resins having an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.
  • All or some of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent evaporation of the active compounds and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder employed).
  • The plasticizers originate 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, glycerol ethers or higher molecular weight glycol ethers, glycerol esters and p-toluenesulphonic acid esters.
  • Fixing agents are based chemically on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl ether or ketones, such as benzophenone or ethylenebenzophenone.
  • Possible solvents or diluents are, in particular, also water, if appropriate as a mixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersing agents.
  • Particularly effective preservation of wood is achieved by impregnation processes on a large industrial scale, for example vacuum, double vacuum or pressure processes.
  • The ready-to-use compositions can also comprise other insecticides, if appropriate, and also one or more fungicides, if appropriate.
  • Possible additional mixing components are, preferably, the insecticides and fungicides mentioned in WO 94/29 268. The compounds mentioned in this document are an explicit constituent of the present application.
  • Especially preferred mixing partners which may be mentioned are insecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron, and also fungicides, such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.
  • The active compounds according to the invention can be used particularly effectively for controlling plant-damaging insects, such as, for example, against the larvae of the mustard beetle (Phaedon cochleariae), against the larvae of the green rice leafhopper (Nephotettix cincticeps) and against the larvae of the green peach aphid (Myzus persicae).
  • In addition to the acaricidal, herbicidal and insecticidal properties described, a fungicidal activity of the active compounds according to the invention is noticeable. In both ‘in vitro’ and ‘in vivo’ studies, a broad fungicidal effect can be observed.
  • Moreover, it was noticed that the active compounds are, in particular, also suitable for controlling mildew, leaf blotch and Fusaria on the infected plants.
  • The preparation and the use of the active compounds according to the invention is shown in the examples below.
    • PREPARATION EXAMPLES Example 1
  • Figure US20060100106A1-20060511-C00061
    (Process C)
  • At 60° C., a mixture of 0.9 g of 4-chlorobenzoylacetonitrile and trimethyl formate is admixed with 0.3 g of isopropylamine. The reaction mixture is heated at 125-130° C., and the reaction is monitored by thin-layer chromatography.
  • After all of the starting material has been converted, the reaction mixture is concentrated using a rotary evaporator, and the product that has been formed is extracted using methylene chloride/NaHCO3 solution.
  • The compounds contained in the solution were separated by column chromatography on a silica gel phase using the mobile phase hexane/ethyl acetate (2:1).
  • One of the main fractions gave, after evaporation of the solvent, 0.65 g (yield 55% of theory) of 2-(4-chlorobenzoyl)-3-(N-methylamino)-propenonitrile of melting point 148° C.
    • Example 2
  • Figure US20060100106A1-20060511-C00062
    (Process A)
  • A mixture of 0.7 g of 4-chloro-benzoylacetonitrile, 0.5 g of methyl N-methyliminoacetate and 8 ml of toluene is initially charged and heated at 80° C. The reaction mixture is stirred at 80° C. for 10 hours and then concentrated by evaporating the solvent, and the precipitated solid is recrystallized from methyl t-butyl ether/di-chloromethane.
  • This gives 0.51 g (yield 54.9% of theory) of 2-(4-chlorobenzoyl)-3-(N-methylamino)-crotononitrile of melting point 152° C.
    • Example 3
  • Figure US20060100106A1-20060511-C00063
    (Process A)
  • 1 g of thiomethyl N-methyl-4-chloroiminobenzoate and 1 g of 4-chlorobenzoylaceto-nitrile are added to 10 ml of toluene. The mixture is stirred for 4 hours. After complete conversion (TLC), the components contained in the mixture are separated by column chromatography on a silica gel phase using the mobile phase hexane/ethyl acetate (2:1).
  • One of the main fractions gave, after evaporation of the solvent, 1.30 g (yield 81% of theory) of 2-(4-chlorobenzoyl)-3-(4-chlorophenyl)-3-(N-methylamino)-propenonitrile of melting point 182° C.
    • Example 4
  • Figure US20060100106A1-20060511-C00064
  • At 0° C., 5 g of N-methyl-4-chloro-thiobenzamide are dissolved in acetonitrile and admixed with 3.3 g of potassium hydroxide. At a temperature of 20° C., 4 g of methyl iodide are added, and the mixture is then heated at 60° C. After complete conversion (TLC), the reaction mixture is filtered and concentrated by evaporation of the solvent using a rotary evaporator.
  • This gave 2.0 g (yield 40% of theory) of thiomethyl N-methyl-4-chloroiminobenzoate, which decomposes readily.
    • Example 5
  • Figure US20060100106A1-20060511-C00065
  • At 0° C., 80 g of the compound N-methyl-4-chloro-benzamide in 600 ml of pyridine are admixed with 107 g of phosphorus pentasulphide. The mixture is heated to 80° C. and then kept at this temperature for 2 hours.
  • The components contained in the mixture were separated by column chromatography on a silica gel phase using the mobile phase hexane/ethyl acetate (10:1).
  • One of the main fractions gave, after evaporation of the solvent, 46 g of N-methyl-4-chloro-thiobenzamide (yield 52% of theory).
    • Example 6
  • Figure US20060100106A1-20060511-C00066
  • At −30° C., about 200 ml of methylamine are condensed into 400 ml of THF. At from −10° C. to 0° C., the reaction solution is then admixed with 75 g of 4-chlorobenzoyl chloride (as a solution in 30 ml of THF). At 20° C., the further progress of the reaction is monitored by thin-layer chromatography.
  • After complete conversion, the compounds contained in the mixture are separated by column chromatography on a silica gel phase using the mobile phase hexane/ethyl acetate (2: 1).
  • The main fraction gave, after evaporation of the solvent, 80 g (yield 99% of theory) of N-methyl-4-chloro-benzamide.
    • Example 7
  • Figure US20060100106A1-20060511-C00067
  • 1 g of 4-chlorobenzoyl-acetamide (known from JP-A 89-108491) and 10 ml of trimethyl orthoformate are mixed and reacted at 90° C. for one hour. After cooling to 60° C., 2 ml of i-propylamine are added. The mixture is then heated at 110° C. for 10 minutes. After complete conversion, the compounds contained in the mixture are separated by column chromatography on a silica gel phase using the mobile phase hexane/ethyl acetate (2:1).
  • The main fraction gave, after evaporation of the solvent, 0.2 g (yield 7.5% of theory) of 2-(4-chlorobenzoyl)-3-(N-isopropylamino)-propenamide.
      • 1H-NMR (400 MHz, d6-DMSO): δ=1.14 (d, 6H, CH(CH 3 )2), 3.58 (m, 1H, CH(CH3)2), 7.16 (d, br, 1H, CONH), 8.86 (d, br, 1H, CONH), 10.83 (br, 1H, NH) ppm,
      • UV (acetonitrile/H3PO4 buffer gradient): λmax244, 292 nm.
    Example 8
  • Figure US20060100106A1-20060511-C00068
    (Process D)
  • At a temperature of 20° C., 0.8 g of 2-(4-chlorobenzoyl)-3-(N-cyclopropylamino)-crotononitrile is admixed with 0.7 g of Lawesson's reagent and reacted for one hour. After complete conversion, the components contained in the mixture are separated by column chromatography on a silica gel phase using the mobile phase hexane/ethyl acetate (2: 1).
  • The main fraction gave, after evaporation of the solvent, 0.7 g (yield 84% of theory) of 2-[(4-chlorophenyl)-thiocarbonyl]-3-(N-cyclopropylamino)-crotononitrile of melting point 215° C.
    • Example 9
  • Figure US20060100106A1-20060511-C00069
  • 30.0 g of 6-fluoro-4H-benz[1,4]oxazin-3-one are initially charged in 300 ml of dichloromethane, and 37.4 g of bromine are then slowly added dropwise at room temperature. The mixture is heated at 30° C. with stirring for 15 h. The reaction solution is cooled to room temperature and poured onto ice. The aqueous phase is extracted repeatedly with dichloromethane. The combined organic phases are washed with saturated sodium thiosulphate solution, dried over magnesium sulphate and concentrated. This give 44.1 g (yield 99.5% of theory) of 7-bromo-6-fluoro-4H-benz[1,4]oxazin-3-one of melting point 244° C.
    • Example 10
  • Figure US20060100106A1-20060511-C00070
  • Under argon, 25.5 g of 7-bromo-6-fluoro-4H-benz[1,4]oxazin-3-one are initially charged in 120 ml of DMF and, at 0° C., admixed a little at a time with 28.0 g of potassium carbonate. At 0° C., 13.0 ml of allyl bromide are then added dropwise, and the mixture is stirred at room temperature for 15 h. The mixture is poured into 1 200 ml of ice-water and extracted repeatedly with ethyl acetate, and the combined organic phases are washed with saturated aqueous sodium chloride solution, dried over magnesium sulphate and concentrated.
  • The crude product is purified by silica gel column chromatography (mobile phase: ethyl acetate/cyclohexane 1:1), giving 23.8 g (yield 81.9% of theory) of N-allyl-7-bromo-6-fluoro-4H-benz[1,4]oxazin-3-one of melting point 92° C.
    • Example 11
  • Figure US20060100106A1-20060511-C00071
  • 20.0 g of N-benzyl-7-methoxycarbonyl-4H-benz[1,4]oxazin-3-one are initially charged in 750 ml of MeOH. At room temperature, 35 ml of 2N aqueous sodium hydroxide solution are added dropwise, and the mixture is stirred at 40-55° C. for 30 h. The reaction solution is cooled to room temperature and poured into a mixture of 200 ml of 1N HCl and 1 kg of ice. The crude product is filtered off with suction, washed with water and dried. This gives 18.2 g (yield 95.5% of theory) of N-benzyl-7-hydroxycarbonyl-4H-benz[1,4]oxazin-3-one of melting point 230° C.
  • The following compounds are obtained analogously to the preparation examples and in accordance with the general statements on the preparation of compounds of the formula (I):
    TABLE 1
    (I-a)
    Figure US20060100106A1-20060511-C00072
    Comp. No. Gn Y Z m.p. ° C.
    I-a-1 4-Cl i-C3H7 H 148
    I-a-2 4-Cl
    Figure US20060100106A1-20060511-C00073
         		H 119
    I-a-3 3,5-(CF3)2 C2H5 H 78-80
    I-a-4 3,5-(CF3)2 CH3 H 150
    I-a-5 3,5-(CF3)2 H H 149
    I-a-7 4-Cl CH3 H 208
    I-a-8 4-Cl
    Figure US20060100106A1-20060511-C00074
         		H 138
    I-a-9 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00075
         		H 110
    I-a-10 4-Cl F3C—CH2— H 155
    I-a-11 3,5-(CF3)2 F3C—CH2— H 154
    I-a-12 3,5-(CF3)2 i-C3H7 H 134
    I-a-13 4-Cl
    Figure US20060100106A1-20060511-C00076
         		CH3 58-60
    I-a-14 4-Cl i-C3H7 CH3 137
    I-a-15 3,5-(CF3)2 i-C3H7 CH3 118-120
    I-a-16 3,5-(CF3)2 C2H5 CH3 oil
    I-a-17 3,5-(CF3)2 CH3 CH3 oil
    I-a-18 3,5-(CF3)2 H CH3 172-174
    I-a-19 4-Cl H CH3 162
    I-a-20 4-Cl CH3 CH3 171
    I-a-21 4-Cl F3C—CH2 CH3 145
    I-a-22 3,5-(CF3)2 F3C—CH2 CH3 122
    I-a-23 4-Cl
    Figure US20060100106A1-20060511-C00077
         		CH3 82-84
    I-a-24 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00078
         		CH3 78-80
    I-a-25 4-Cl i-C3H7 C2H5 162
    I-a-26 3,5-(CF3)2 C2H5 C2H5 105
    I-a-27 4-Cl CH3 C2H5 149
    I-a-28 3,5-(CF3)2 i-C3H7 n-C3H7 83
    I-a-29 4-Cl i-C3H7 n-C3H7 102
    I-a-30 3,5-(CF3)2 CH3 n-C3H7 oil
    I-a-31 3,5-(CF3)2 C2H5 n-C3H7 oil
    I-a-32 3,5-(CF3)2 i-C3H7 n-C4H9 73
    I-a-33 3,5-(CF3)2 C2H5 n-C4H9 oil
    I-a-34 3,5-(CF3)2 CH3 n-C4H9 oil
    I-a-35 4-Cl i-C3H7 n-C4H9 60
    I-a-36 4-Cl H
    Figure US20060100106A1-20060511-C00079
         		270
    I-a-37 4-Cl H
    Figure US20060100106A1-20060511-C00080
         		242
    I-a-38 4-Cl i-C3H7
    Figure US20060100106A1-20060511-C00081
         		144
    I-a-39 3,5-(CF3)2 H
    Figure US20060100106A1-20060511-C00082
         		146
    I-a-40 3,5-(CF3)2 H
    Figure US20060100106A1-20060511-C00083
         		182
    I-a-42 3,5-(CF3)2 CH3
    Figure US20060100106A1-20060511-C00084
         		170
    I-a-43 4-Cl i-C3H7
    Figure US20060100106A1-20060511-C00085
         		150
    I-a-44 4-Cl i-C3H7
    Figure US20060100106A1-20060511-C00086
         		146-148
    I-a-45 4-Cl C2H5
    Figure US20060100106A1-20060511-C00087
         		135
    I-a-46 3,5-(CF3)2 C2H5
    Figure US20060100106A1-20060511-C00088
         		132-134
    I-a-47 3,5-(CF3)2 i-C3H7
    Figure US20060100106A1-20060511-C00089
         		138-140
    I-a-48 3,5-(CF3)2 i-C3H7
    Figure US20060100106A1-20060511-C00090
         		152
    I-a-49 3,5-(CF3)2 C2H5
    Figure US20060100106A1-20060511-C00091
         		182
    I-a-50 3,5-(CF3)2 CH3
    Figure US20060100106A1-20060511-C00092
         		173
    I-a-51 3,S-(CF3)2 C2H5
    Figure US20060100106A1-20060511-C00093
         		147
    I-a-52 3,S-(CF3)2 CH3
    Figure US20060100106A1-20060511-C00094
         		139
    I-a-53 4-Cl C2H5
    Figure US20060100106A1-20060511-C00095
         		133
    I-a-54 3,5-(CF3)2 i-C3H7
    Figure US20060100106A1-20060511-C00096
         		136-138
    I-a-55 3,5-(CF3)2 C2H5
    Figure US20060100106A1-20060511-C00097
         		138
    I-a-56 3,5-(CF3)2 CH3
    Figure US20060100106A1-20060511-C00098
         		148
    I-a-57 4-Cl i-C3H7
    Figure US20060100106A1-20060511-C00099
         		oil
    I-a-58 2,4-F2 CH3 CH3 146
    I-a-59 4-Cl CH3 CH3 152
    I-a-60 4-Cl i-C3H7 H
    I-a-61 3,5-(CF3)2 CH(CH3)2 C2H5 123
    I-a-62 4-Cl CH(CH3)2
    Figure US20060100106A1-20060511-C00100
         		oil
    I-a-63 4-Cl
    Figure US20060100106A1-20060511-C00101
         		CH3 113
    I-a-64 2-F, 4-Cl, 5-O-allyl
    Figure US20060100106A1-20060511-C00102
         		CH3 83
    I-a-65 4-Cl
    Figure US20060100106A1-20060511-C00103
         		CH3 124
    I-a-66 4-Cl n-C3H7 CH3 134
    I-a-67 4-Cl CH2CH(CH3)2 CH3 120
    I-a-68 4-Cl C(CH3)3 CH3 123
    I-a-69 4-Cl CH2C(CH3)3 CH3 147
    I-a-70 4-Cl
    Figure US20060100106A1-20060511-C00104
         		CH3 oil
    I-a-71 4-Cl
    Figure US20060100106A1-20060511-C00105
         		CH3 oil
    I-a-72 4-Cl
    Figure US20060100106A1-20060511-C00106
         		CH3 134
    I-a-73 3,5-(CF3)2 CH2CH(CH3)C2H5 CH3 oil
    I-a-74 4-Cl cyclo-C5H9 CH3 98
    I-a-75 4-Cl CH2CH(CH3)C2H5 CH3 oil
    I-a-76 4-Cl C(CH3)2CH2C(CH3)3 CH3 99
    I-a-77 4-Cl C(CH3)2(CN) CH3 143
    I-a-78 4-Cl C(C2H5)2C≡CH CH3 oil
    I-a-79 4-Cl C(CH3)2C≡CH CH3 95
    I-a-80 4-Cl C(CH3)2C2H5 CH3 oil
    I-a-81 4-Cl
    Figure US20060100106A1-20060511-C00107
         		H 124
    I-a-82 3,5-(CF3)2 CH2CH═CH2 H 99
    I-a-83 2-F, 4-Cl, CH(CH3)2 H oil
    5-O-allyl
    I-a-84 2-F, 4-Cl,
    Figure US20060100106A1-20060511-C00108
         		H 143
    5-0-allyl
    I-a-85 2-F, 4-Cl, CH3 H 162
    5-O-allyl
    I-a-86 2-F, 4-CN, CH3 H 158
    5-O-benzyl
    I-a-87 4-Cl
    Figure US20060100106A1-20060511-C00109
         		H 133
    I-a-88 4-Cl n-C3H7 H 108
    I-a-89 4-Cl CH2CH(CH3)2 H 123
    I-a-90 4-Cl C(CH3)3 H 125
    I-a-91 4-Cl CH2C(CH3)3 H 121
    I-a-92 4-Cl
    Figure US20060100106A1-20060511-C00110
         		H oil
    I-a-93 4-Cl
    Figure US20060100106A1-20060511-C00111
         		H oil
    I-a-94 3,5-(CF3)2 CH(CH3)C2H5 H 146
    I-a-95 4-Cl C(CH3)2CH2OH CH3 oil
    I-a-96 4-Cl C(CH3)2CH(CH3)CH2OH CH3 181
    I-a-97 4-Cl C(C3H6OH)3 CH3 oil
    I-a-98 4-Cl
    Figure US20060100106A1-20060511-C00112
         		CH3 oil
    I-a-99 4-Cl
    Figure US20060100106A1-20060511-C00113
         		CH3 oil
    I-a-100 4-Cl
    Figure US20060100106A1-20060511-C00114
         		CH3 oil
    I-a-101 4-Cl
    Figure US20060100106A1-20060511-C00115
         		CH3 wax
    I-a-102 4-Cl
    Figure US20060100106A1-20060511-C00116
         		CH3 wax
    I-a-103 4-Cl
    Figure US20060100106A1-20060511-C00117
         		CH3 191
    I-a-104 4-Cl
    Figure US20060100106A1-20060511-C00118
         		CH3 wax
    I-a-105 4-Cl
    Figure US20060100106A1-20060511-C00119
         		CH3 oil
    I-a-106 4-Cl
    Figure US20060100106A1-20060511-C00120
         		CH3 oil
    I-a-107 4-Cl
    Figure US20060100106A1-20060511-C00121
         		CH3 105
    I-a-108 4-Cl
    Figure US20060100106A1-20060511-C00122
         		CH3 oil
    I-a-109 4-Cl
    Figure US20060100106A1-20060511-C00123
         		CH3 oil
    I-a-110 4-Cl
    Figure US20060100106A1-20060511-C00124
         		CH3 199
    I-a-111 4-Cl
    Figure US20060100106A1-20060511-C00125
         		CH3 121
    I-a-112 4-Cl
    Figure US20060100106A1-20060511-C00126
         		CH3 193
    I-a-113 4-Cl
    Figure US20060100106A1-20060511-C00127
         		CH3 oil
    I-a-114 4-Cl
    Figure US20060100106A1-20060511-C00128
         		CH3 oil
    I-a-115 4-Cl
    Figure US20060100106A1-20060511-C00129
         		CH3 119
    I-a-116 4-Cl
    Figure US20060100106A1-20060511-C00130
         		CH3 wax
    I-a-117 4-Cl
    Figure US20060100106A1-20060511-C00131
         		CH3 oil
    I-a-118 4-Cl
    Figure US20060100106A1-20060511-C00132
         		CH3 oil
    I-a-119 4-Cl
    Figure US20060100106A1-20060511-C00133
         		CH3 oil
    I-a-120 4-Cl
    Figure US20060100106A1-20060511-C00134
         		CH3 wax
    I-a-121 4-Cl
    Figure US20060100106A1-20060511-C00135
         		CH3 146
    I-a-122 4-Cl
    Figure US20060100106A1-20060511-C00136
         		CH3 99
    I-a-123 4-Cl
    Figure US20060100106A1-20060511-C00137
         		CH3 oil
    I-a-124 4-Cl
    Figure US20060100106A1-20060511-C00138
         		CH3 oil
    I-a-125 4-Cl C(CH3)(CH2F)2 CH3 114
    I-a-126 4-Cl C(CH3)2CH2F CH3 106
    I-a-127 4-Cl C(CH3)2CF3 CH3 wax
    I-a-128 4-Cl C(CH2F)3 CH3 oil
    I-a-129 4-Cl C(CHF2)3 CH3 oil
    I-a-130 4-Cl
    Figure US20060100106A1-20060511-C00139
         		CH3 101
    I-a-131 4-Cl
    Figure US20060100106A1-20060511-C00140
         		CH3 oil
    I-a-132 4-Cl
    Figure US20060100106A1-20060511-C00141
         		CH3 wax
    I-a-133 4-Cl
    Figure US20060100106A1-20060511-C00142
         		CH3 oil
    I-a-134 2-F, 4-Cl, 5- C(CH3)3 CH3 119
    O-allyl
    I-a-135 3,5-(CF3)2 CH3
    Figure US20060100106A1-20060511-C00143
         		oil
    I-a-136 4-Cl
    Figure US20060100106A1-20060511-C00144
         		CH3 140
    I-a-137 4-Cl
    Figure US20060100106A1-20060511-C00145
         		CH3 115
    I-a-138 4-Cl
    Figure US20060100106A1-20060511-C00146
         		CH3 oil
    I-a-139 4-Cl
    Figure US20060100106A1-20060511-C00147
         		CH3 oil
    I-a-140 4-Cl
    Figure US20060100106A1-20060511-C00148
         		CH3 oil
    I-a-141 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00149
         		CH3 oil
    I-a-142 3,5-(CF3)2 CH2CH(CH3)2 CH3 oil
    I-a-143 3,5-(CF3)2 C(CH3)3 CH3 oil
    I-a-144 3,5-(CF3)2 CH2C(CH3)3 CH3 oil
    I-a-145 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00150
         		CH3 oil
    I-a-146 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00151
         		CH3 oil
    I-a-147 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00152
         		CH3 oil
    I-a-148 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00153
         		CH3 oil
    I-a-149 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00154
         		CH3 oil
    I-a-150 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00155
         		CH3 oil
    I-a-151 3,5-(CF3)2 cyclo-C5H9 CH3 oil
    I-a-152 3,5-(CF3)2 n-C3H7 CH3 oil
    I-a-153 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00156
         		CH3 oil
    I-a-154 4-Cl
    Figure US20060100106A1-20060511-C00157
         		H 131
    I-a-155 4-Cl
    Figure US20060100106A1-20060511-C00158
         		H oil
    I-a-156 4-Cl
    Figure US20060100106A1-20060511-C00159
         		H
    I-a-157 4-Cl CH2CH(CH3)C2H5 H 84
    I-a-158 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00160
         		H 131
    I-a-159 3,5-(CF3)2 cyclo-C6H11 H 158
    I-a-160 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00161
         		H 124
    I-a-161 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00162
         		H 149
    I-a-162 3,5-(CF3)2 n-C3H7 H 119
    I-a-163 3,5-(CF3)2 CH2CH(CH3)2 H 144
    I-a-164 3,5-(CF3)2 C(CH3)3 H 123
    I-a-165 3,5-(CF3)2 CH2C(CH3)3 H 139
    I-a-166 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00163
         		H oil
    I-a-167 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00164
         		H oil
    I-a-168 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00165
         		H 95
    I-a-169 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00166
         		H 102
    I-a-170 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00167
         		H oil
    I-a-171 3,5-(CF3)2
    Figure US20060100106A1-20060511-C00168
         		H 134
    I-a-172 3,5-(CF3)2 CH2CH(CH3)C2H5 H 119
  • In the Tables, “Me” denotes a methyl group (CH3).
  • The following compound is obtained analogously to the preparation examples and in accordance with the general statements on the preparation of compounds of formula (I) in the description:
    TABLE 2
    (I-b)
    Figure US20060100106A1-20060511-C00169
    Comp. No. Y Z m.p. ° C.
    I-b-1 C(CH3)3 CH3 oil
  • The following compounds are obtained analogously to Preparation Example 4 and in accordance with the general statements on the preparation of compounds of the formula (III):
    (III-a)
    Figure US20060100106A1-20060511-C00170
    Comp. No. R8 Y Rg m.p. ° C.
    III-a-1 CH3 CH3 4-Cl oil
    III-a-2 CH3 allyl H oil
    III-a-3 CH3 allyl 4-Cl oil
    III-a-4 CH3 i-C3H7 4-Cl oil
    III-a-5 CH3 C2H5 4-Cl oil
    III-a-6 CH3 CH2—CF3 4-Cl oil
  • The following compounds are obtained analogously to Preparation Example 5 and in accordance with the general statements on the preparation of compounds of the formula (VI):
    (VI-a-1)
    Figure US20060100106A1-20060511-C00171
    Comp. No. Y Rg
    VI-a-1 CH3 4-Cl
    VI-a-2 i-C3H7 4-Cl
    VI-a-3 allyl 4-Cl
    VI-a-4 C2H5 4-Cl
    VI-a-5 CH2—CF3 4-Cl
    • EXAMPLE
  • Post-Emergence Test
    Solvent: 5 parts by weight of acetone
    Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Test plants of a height of 5-15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. After 3 weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
  • The figures denote:
     0% = no effect (like untreated control)
    100% = total destruction
  • In this test, for example, the compounds of Preparation Examples I-a-35, I-a-20, I-a-4, I-a-17, I-a-3, I-a-59, I-a-58, I-a-29, I-a-8 and I-a-23 exhibit strong activity against weeds, and some are tolerated well by crop plants, such as, for example, wheat.
    • EXAMPLE
  • Pre-Emergence Test
    Solvent: 5 parts by weight of acetone
    Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of active compound. The amount of water per unit area is advantageously kept constant. The concentration of active compound in the preparation is immaterial, only the application rate of active compound per unit area matters. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
  • The figures denote:
     0% = no effect (like untreated control)
    100% = total destruction
  • In this test, for example, the compounds of Preparation Examples I-a-3, I-a-17, I-a-20, I-a-4, I-a-58, I-a-59, I-a-23, I-a-8 and I-a-21 exhibit strong activity against weeds, and some are tolerated well by crop plants, such as, for example, wheat and soya.
    • Example A
  • Meloidogyne Test
    Solvent: 30 parts by weight of dimethylformamide
    Emulsifier:  1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Containers are filled with sand, solution of active compound, Meloidogyne incognita egg/larvae suspension and lettuce seeds. The lettuce seeds germinate and the plants develop. On the roots, galls are formed.
  • After the desired period of time, the nematicidal action is determined in % using gall formation as a measure. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to that on the untreated control.
  • In this test, for example, the following compounds of the preparation examples exhibit good activity:
    • I-a-39, I-a-42, I-a-5
    Example B
  • Phaedon Larvae Test
    Solvent: 30 parts by weight of dimethylformamide
    Emulsifier:  1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing 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 are populated with larvae of the mustard beetle (Phaedon cochleariae) while the leaves are still moist.
  • After the desired period of time, the kill in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
  • In this test, for example, the following compounds of the preparation examples show good activity:
    • I-a-13, I-a-49, I-a-44, I-a-15, I-a-19, I-a-53
    Example C
  • Plutella Test
    Solvent: 30 parts by weight of dimethylformamide
    Emulsifier:  1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing 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 are populated with caterpillars of the owlet moth (Plutella xylostella) while the leaves are still moist.
  • After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
  • in this test, for example, the following compounds of the preparation examples show good activity:
    • I-a-58, I-a-45
    Example D
  • Spodoptera Grugiperda Test
    Solvent: 30 parts by weight of dimethylformamide
    Emulsifier:  1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing 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 are populated with caterpillars of the armyworm (Spodoptera frugiperda) while the leaves are still moist.
  • After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
  • In this test, for example, the following compounds of the preparation examples show good activity:
    • I-a-42, I-a-45, I-a-48, I-a-18, I-a-52
    Example E
  • Tetranychus Test (OP-Resistant/Dip Treatment)
    Solvent: 7 parts by weight of dimethylformamide
    Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Bean plants (Phaseolus vulgaris) which are heavily infested by all stages of the greenhouse red spider mite (Tetranychus urticae) are dipped into a preparation of active compound of the desired concentration.
  • After the desired period of time, the effect in % is determined. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.
  • In this test, for example, the following compounds of the preparation examples show good activity:
    • I-a-3

Claims (3)

1-10. (canceled)
11. The compound of formula (I)
Figure US20060100106A1-20060511-C00172
wherein
K represents oxygen or sulphur,
Ar represents Ar1, where Ar1 represents phenyl which is mono- to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, s-, n-, i- or t-butyl, methoxy, ethoxy, propoxy, i-propoxy, s-, n-, i- or t-butoxy, allyloxy, methallyloxy, 2-butenyloxy, propargyloxy, 2-butinyloxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylenedioxy, tetrafluoroethylenedioxy, difluoromethylthio, trifluoromethylthio, trifluoro-methylsulphinyl, trifluoromethylsulphonyl, benzyloxy, hydroxyl, mercapto, cyano or amino, or represents pyridyl which is mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, methylthio, ethylthio or trifluoromethyl,
 or represents Ar2, where Ar2 represents Ar1 which is additionally substituted by phenyl, pyridyl, thienyl, tetrazolyl, triazolyl or phenoxy, where these substituents are for their part mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, s-, n-, i- or t-butyl, methoxy, ethoxy, i-propoxy, s-, n- or t-butoxy, trifluoromethyl, trifluoromethoxy, nitro or cyano,
 or represents the group
Figure US20060100106A1-20060511-C00173
 where B1 represents hydrogen or fluorine and B8 represents allyl, propargyl or benzyl,
X represents
Figure US20060100106A1-20060511-C00174
Y represents hydrogen, in each case optionally mono- or poly-hydroxy-substituted C1-C6-alkyl, C1-C4-halogenoalkyl, C3-C6-alkenyl, C3-C6-alkinyl, C1-C4-alkoxy-C2-C3-alkyl, di-C1-C2-alkoxy-C2-C4-alkyl, C1-C2-alkoxy-C2-C4-cyanoalkyl, C1-C2-alkylthio-C2-C3-alkyl, C1-C5-halogenoalkenyl or C1-C6-cyanoalkyl, represents in each case optionally methyl-, methoxy-, ethoxy-, trifluoromethyl-, cyano-, chlorophenyl-, benzyl-, hydroxymethyl-, fluorine- or chlorine-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C2-alkyl in which optionally one methylene group may be replaced by oxygen or sulphur, represents benzyl, phenethyl or pyridylmethyl, each of which is optionallymono- to trisubstituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro,
Z represents hydrogen, methyl, ethyl, represents phenyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
R3 represents methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl, vinyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, n-, s-, i- or t-butyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cyclopentyloxy, cyclohexyloxy, represents phenyl, pyridyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, n-, s-, i- or t-butyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro, or in the case of the radicals a), c) and f) mentioned under Ar, also represents the group
Figure US20060100106A1-20060511-C00175
R5 represents hydrogen or methyl,
R6 represents hydrogen, methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, represents phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
R7 represents hydrogen, methyl or ethyl, or
R6, R7 furthermore together with the nitrogen atom to which they are attached represent a pyrrolidine, piperidine or morpholine radical;
provided that the compound of formula (I) is not:
(a) wherein K is O, Ar is p-fluorophenyl, X is CN, Z is methyl, and Y is hydrogen or methyl or n-butyl; or
(b) wherein K is O, Ar is 2,4-dichloro-5-fluorophenyl or 2,4-dichlorophenyl, X is CN, Z is hydrogen, and Y is cyclopropyl.
12. The compound according to claim 11, wherein
K represents oxygen,
Ar represents phenyl which is mono- or polysubstituted by trifluoromethyl, fluorine, chlorine, allyloxy, cyano, benzyloxy, or represents the group
Figure US20060100106A1-20060511-C00176
 where particular emphasis is given to the meanings 4-chlorophenyl, 3,5-di(trifluoromethyl)phenyl and 2-fluoro-4-chloro-5-allyloxy,
X represents CN,
Y represents hydrogen, C1-C6-alkyl, C1-C3-halogenoalkyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl,
Z represents hydrogen or methyl.
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