WO2003059903A2 - Substituted 4-aminopyridine derivatives used as pest control agents - Google Patents

Abstract

The invention relates to the novel substituted 4-aminopyridine derivatives of formula (I), wherein R1, R2, Het, n, Y and p are defined as in the description. The invention also relates to several methods for producing said derivatives and to the use thereof in pest control, to novel intermediate products and to methods for producing the same.

Description

Substituted 4-aminopyridine derivatives

The present invention relates to new substituted 4-aminopyridine derivatives, processes for their preparation and their use as pesticides and for controlling unwanted microorganisms.

It is already known that certain substituted 4-aminopyridines have insecticidal properties (cf. e.g. WO 93/04580, WO 96/08475, WO 96/10016 or WO 96/33975). However, the effectiveness or range of action of these compounds is not always completely satisfactory, especially when low amounts and concentrations are applied.

New substituted 4-aminopyridine derivatives of the formula (I) have been found

in which

R ^{1 represents} alkyl,

R ^{2 represents} halogen,

Het represents an optionally substituted heterocycle,

n represents 1 or 2,

Y stands for halogen, alkyl or haloalkyl and p stands for 0, 1 or 2.

Furthermore, it was found that the substituted 4-aminopyridine derivatives of the formula (I) can be obtained by a) 4-aminopyridines of the formula (11)

in which

R ¹ and R ^{2 have} the meanings given above,

and phenylacetic acids of the formula (IE)

in which

Het, Y, n and p have the meanings given above,

(1) with a halogenating agent, preferably thionyl chloride, optionally in the presence of an acid binding agent and optionally in the presence of a diluent; or

(2) in the presence of a carboxyl group activating catalyst and in the presence of a diluent; or

b) substituted 4-aminopyridines of the formula (TV)

in which

R and R have the meanings given above and

Q represents a leaving group, with bromides of the formula (V)

in which

Het, Y and p have the meanings given above and m represents 0 or 1,

in the presence of a base, in the presence of a catalyst and in the presence of a diluent; or c) substituted 4-aminopyridines of the formula (VT)

in which

R and R have the meanings given above,

with compounds of the formula (VE)

in which

Het, Q, Y, m and p have the meanings given above,

in the presence of a base, in the presence of a catalyst and in the presence of a diluent. Finally, it was found that the new substituted 4-aminopyridine derivatives of the formula (I) have highly pronounced biological properties and above all to control animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forests and in stock - and material protection as well as in the hygiene sector, and are suitable for combating undesirable microorganisms.

The 4-aminopyridine derivatives according to the invention are generally defined by the formula (I).

Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below:

R ¹ is preferably C _\ -C ₄ - alkyl. R ² preferably represents fluorine, chlorine, bromine or iodine.

Het preferably represents an optionally mono- or polysubstituted, identically or differently substituted 5- or 6-membered heterocycle having 1 to 4 heteroatoms, such as N, O or S, examples of which may be mentioned as substituents:

Halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, cyano, nitro, formyl, hydroxyimino, AKkoxyimino, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, optionally substituted phenyl, optionally substituted morpholino or optionally substituted tetrazolyl.

n is preferably 1 or 2.

Y preferably represents fluorine, chlorine, bromine; C ₁ -C ₄ alkyl or dC ₄ - haloalkyl, p preferably represents 0, 1 or 2. R ¹ is particularly preferably C ₁ -C ₂ -alkyl.

R ² particularly preferably represents fluorine, chlorine or bromine.

Het particularly preferably represents 5- or 6-membered heterocycles from the series of thienyl, oxazolyl, isoxazolyl, pyrazolyl; 1,2,4-oxadiazolyl; 1,2,4-thia-diazolyl; 1,3,4-thiadiazolyl; Tetrazolyl, pyridinyl, pyrimidinyl or pyridonyl, each of which can be substituted one to three times (depending on the respective substitution options), identically or differently, examples of such substituents being: fluorine, chlorine, bromine, iodine; Gi alkyl; Cι-C ₄ alkoxy, C ₁ -C ₄ alkylthio; each one to five times, the same or different, substituted by fluorine or chlorine substituted Ci- -alkyl, Cr -alkoxy and CrC -alkylthio; Cyano, nitro, formyl, hydroxyimino, C ₁ -C alkyl: oxyirnino, C ₁ -C alkylcarbonyl, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkoxycarbonyl-C ₁ -C alkyl; optionally single to triple, identical or different, by fluorine, chlorine, bromine, C ₁ -C ₄ alkyl,

C ₁ -C ₄ haloalkyl, alkoxy, C ₁ -C ₄ haloalkoxy, nitro or cyano substituted phenyl; optionally single to triple, identical or different, fluorine, chlorine, bromine or -C ₄ alkyl substituted morpholino or optionally substituted by C ₁ -C alkyl tetrazolyl.

n particularly preferably represents 1 or 2.

Y particularly preferably represents fluorine, chlorine, methyl or trifluoromethyl. p particularly preferably represents 0, 1 or 2.

R ¹ very particularly preferably represents ethyl.

R ² very particularly preferably represents chlorine.

Het very particularly preferably represents 5- or 6-membered heterocycles from the

Series of thienyl, oxazolyl, isoxazolyl, pyrazolyl; 1,2,4-oxadiazolyl; 1,2,4-thiadiazolyl; 1,3,4-thiadiazolyl; Tetrazolyl, pyridinyl, pyrimidinyl or

Pyridonyl, each one to three times (depending on the respective substitution options), may be substituted identically or differently, examples of which may be mentioned as substituents: fluorine, chlorine, bromine; Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl; Methoxy, ethoxy, n- or i-propoxy; Methylthio, ethylthio, n- or i-propylthio; Trifluoromethyl, difluoromethyl, fluoromethyl; Trifluoromethoxy, difluoromethoxy; trifluoromethylthio; Cyano, formyl, hydroximino, methoxyimino, ethoxyimino; Methylcarbonyl, ethylcarbonyl; Methoxycarbonyl, ethoxycarbonyl; Methoxycarbonyl-methyl, 1-methoxycarbonyl-1-ethyl; phenyl optionally substituted once or twice, identically or differently by fluorine, chlorine, methyl, methoxy, trifluoromethyl, nitro or cyano; optionally mono- or disubstituted, identically or differently, fluorine, chlorine, methyl or ethyl-substituted mo holino or optionally substituted by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl.

n very particularly preferably represents 1 or 2. p very particularly preferably represents 0.

Also preferred are 4-aminopyridine derivatives of the formula (I) in which R ^{1 is}

Chlorine stands. Also preferred are 4-aminopyridine derivatives of the formula (I) in which R ^{2 is}

Ethyl stands.

Also preferred are 4-anopyridine derivatives of the formula (I) in which p is

0 stands.

Also preferred are 4-aminopyridine derivatives of the formula (I) in which Het represents a 5- or 6-membered heterocycle having at least one nitrogen atom.

The aforementioned radical definitions can be combined with one another in any way. In addition, individual definitions can also be omitted.

The radical definitions listed in the above and below are carbon residues, such as alkyl - also in combination with heteroatoms, such as alkoxy - as far as possible, in each case straight-chain or branched.

If, for example, 2-ethyl-3-chloro-4-aminopyridine and 4- (2-tert-butyl-tetrazol-5-yl) -phenyl-acetic acid and thionyl chloride are used as starting materials, the course of the reaction of the process according to the invention ( a, variant 1) can be represented by the following formula:

If, for example, 4- (4-cyano-pyrazol-l-yl) phenylacetic acid and 2-

Etnyl-3-chloro-4-arninopyridine as starting materials and N, N-carbonyl-bisimidazole as catalyst, the course of the reaction of the process according to the invention (a, variant 2) can be represented by the following formula:

For example, 4- (4,4,5,5-tetramethyl-l, 3,2-dioxaborolan-2-yl) phenylacetic acid-N- (2-ethyl-3-chloropyridin-4-yl) amide is used and 2-methoxy-5-bromopyridine as starting materials, the course of the reaction of process (b) according to the invention can be represented by the following formula:

If, for example, 4-bromo-phenylacetic acid-N- (2-ethyl-3-cMor-pyridin-4-yl) -amide and 2-methoxy-pyridin-5-yl-boronic acid are used as starting materials, the reaction procedure of the process according to the invention can be carried out (c) are represented by the following formula scheme:

The starting materials for carrying out process (a) according to the invention The 4-aminopyridines used are generally defined by the formula (E). In this formula, R and R are preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred or very particularly preferred for these radicals in connection with the description of the compounds of the formula (I) according to the invention ,

The 4-aminopyridines of the formula (E) are generally known compounds of organic chemistry.

Formula (ET) provides a general definition of the phenylacetic acids to be used as starting materials in process (a) according to the invention. In this formula, Het, n, Y and p are preferred, particularly preferred or very particularly preferred for those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred, particularly preferred or entirely for these radicals were particularly preferred.

The phenylacetic acids of the formula (ET) are new and also the subject of this application. They are obtained by building up the heterocyclic radical on the correspondingly substituted phenyl in a known manner.

For example, the 4-tetrazolylphenylacetic acids are obtained by mixing 4-cyanophenylacetic acid with sodium azide in the presence of an amine hydrochloride (for example ammonium chloride or trialkylammonium chloride) and in the presence of an inert organic solvent (for example toluene) at temperatures between 50 ° C. and 150 ° C., preferably between 80 ° C and 120 ° C (see also the manufacturing examples). The tetrazolyl radical can then be alkylated in a conventional manner (see also the preparation examples).

The 4-pyrazolylphenylacetic acids are e.g. obtained by using 4-hydrazino-phenylacetic acid hydrochloride with sodium salts of 2-substituted 1-hydroxy-

3,3-dimethoxy-l-propene derivatives in the presence of an inert organic solution means, such as ethanol, at temperatures between 20 ° C and 50 ° C (see also the manufacturing examples).

The formula (TV) generalizes the substituted 4-aminopyridines to be used as starting materials for carrying out process (b) according to the invention

• 1 9 defined. In this formula, R and R are preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned for these radicals in connection with the description of the compounds of the formula (I) according to the invention. Q is preferably B (OH); 4,4,5,5-tetramethyl-l, 3,2-dioxoborolan-2-yl; 5,5-dimethyl-3,2-dioxo-borinan-2-yl; 4,4,6-trimethyl-l, 3,2-di-oxo-borinan-2-yl or l, 3,2-benzodioxoborolan-2-yl.

The substituted 4-aminopyridines of the formula (TV) are new and also the subject of this application. They are obtained by first of all 4-aminopyridines of the formula (E)

in which

R ¹ and R ^{2 have} the meanings given above,

with 4-bromophenylacetic acid of the formula (VTE)

according to the conditions of process (a) and the resulting substituted 4-aminopyridines of the formula (VT)

in which

R ¹ and R ^{2 have} the meanings given above,

with known boron derivatives of the formula (TX)

H - Q (TX) in which Q has the meanings given above,

implemented according to the conditions of process (c) (see also the production examples).

Formula (V) provides a general definition of the bromides to be used as starting materials in process (b) according to the invention. In this formula, Het, Y and p are preferred, particularly preferred or very particularly preferred for those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred, particularly preferred or very particularly preferred for these radicals were mentioned, m preferably represents 0 or 1.

The bromides of the formula (V) are known or can be obtained in a known manner.

The formula (VT) generalizes the substituted 4-aminopyridines to be used as starting materials for carrying out process (c) according to the invention Are defined. In this formula, R and R are preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred or very particularly preferred for these radicals in connection with the description of the compounds of the formula (I) according to the invention ,

The substituted 4-aminopyridines of Foremi (VI) are obtained by reacting 4-ammopyridines of the formula (E) with 4-bromophenylacetic acid in accordance with the conditions of process (a).

Formula (VE) provides a general definition of the compounds to be used as starting materials in process (c) according to the invention. In this formula, Het, Y and p are preferred, particularly preferred or very particularly preferred for those meanings which have been mentioned as preferred, particularly preferred or very particularly preferred for these radicals in connection with the description of the compounds of the formula (I) according to the invention , m preferably represents 0 or 1. Q preferably represents those meanings which have already been mentioned as preferred for these radicals in connection with the description of the 4-aminopyridines of the formula (TV).

The compounds of formula (VE) are obtained by reacting bromides of formula (V) with boron derivatives of formula (TX) in accordance with the conditions of process (c).

All customary inorganic and organic bases are suitable as acid binders when carrying out process (a, variant 1). Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, are preferably usable. Sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, furthermore ammonium hydroxide, ammonium acetate or ammonium carbonate, or tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO) , Diazabicyclonones (DBN) or diazabicycloundecen (DBU).

Suitable diluents for carrying out process (a, variant 1) are all inert, organic solvents. Aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin can preferably be used; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane.

When carrying out process (a, variant 1), the reaction temperatures can be varied within a relatively wide range. In general, temperatures between 0 ° C and + 120 ° C, preferably between 20 ° C and 80 ° C.

When carrying out the process (a, variant 1), one generally works with equimolar amounts or a small excess of halogenating agent and acid binder. The processing takes place according to usual methods. In general, the procedure is such that the reaction mixture is concentrated after the reaction has ended, water and a water-immiscible organic solvent are added to the remaining residue, and the organic phase is separated off, washed, dried and concentrated. The remaining product can be made according to usual

Methods are freed of any contaminants. Suitable catalysts for carrying out process (a, variant 2) are all customary reaction accelerators which are suitable for activating the carboxyl group of the phenylacetic acid derivative of the formula (ET). Carbonyldiimidazole and dicyclohexylcarbodiimide can preferably be used. Furthermore, the reaction can also be carried out in the presence of water-binding agents.

Suitable diluents for carrying out the process (a, variant 2) are all inert organic solvents which are customary for such reactions. Aliphatic, alicyclic or aromatic can preferably be used

Hydrocarbons, such as dioxane, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane.

When the process (a, variant 2) is recycled, the reaction temperatures can be varied within a certain range. In general, temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 80 ° C.

The procedure (a, variant 2) is generally carried out using equimolar amounts. However, it is also possible to use one or the other component in excess. The processing takes place according to usual methods. In general, the procedure is such that the solid which has precipitated is filtered off with suction, the filtrate is concentrated under reduced pressure and the residue which remains is chromatographed.

The diluents used in the process are those of the invention

Processes (b) and '(c) all organic solvents which are inert under the given reaction conditions. They can be mixed with

Water can be used. Hydrocarbons such as are preferably used PT / EP03 / 00051

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Toluene, xylene, tetralin, hexane, cyclohexane, halogenated hydrocarbons such as methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dimethoxyethane, tetiahydrofuran, dioxane, nitriles such as acetonitrile or butyronitrile, amides such as dimethyl formaldehyde, amides such as dimethyl formate.

Suitable bases for carrying out processes (b) and (c) according to the invention are all customary acid acceptors. Tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicyclo- undecene (DBU), diazabicyclonones (DBN), N, N-dimethylaniline, also alkaline earth metal oxides such as magnesium or calcium oxide, and also alkali metal and alkaline earth metal carbonates are preferably usable such as sodium carbonate, potassium carbonate and calcium carbonate, alkali metal hydroxides such as sodium or potassium hydroxide, and also alcoholates such as sodium ethanolate or potassium tert-butoxide.

The catalysts used in carrying out the process according to the invention

(b) and (c) Palladium or its compounds or complexes, preferably tetiakis (triphenylphosphine) palladium or l, r- [bis (diphenylphosphino) ferrocene] dichloropalladium.

The reaction temperatures can be when carrying out the inventive

Processes (b) and (c) can be varied over a wide range. In general, temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 80 ° C or at the boiling point of the solvent used. When recycling processes (b) and (c) according to the invention, the reaction is generally carried out in equimolar amounts, with 0.01 to 0.1 mol being optionally added

Catalyst and 1 to 5 mol of base can be used.

The end products are worked up and isolated in a generally customary manner.

The active ingredients are suitable with good plant tolerance and inexpensive warm Blood toxicity to control animal pests, especially insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stocks and materials as well as in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:

From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber. From the order of the Diplopoda e.g. Blaniulus guttulatus.

From the order of the Chüopoda e.g. Geophilus carpophagus, Scutigera spp ..

From the order of the Symphyla e.g. Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola e.g. Onychiurus armatus. From the order of the Orthoptera e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.

From the order of the Blattaria e.g. Blatta orientalis, Periplaneta americana,

Leucophaea maderae, Blattella germanica.

From the order of the Dermaptera e.g. Forficula auricularia. From the order of the Isoptera e.g. Reticuliterm.es spp ..

From the order of the Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp ..

From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci,

Thrips palmi, Frankliniella accidentalis. From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius,

Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci,

Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabäe, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phoroponosum , Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp. From the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.

Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierilusta s nubilalis, Ephestia kuehmella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana,

Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.

From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diäbrotica spp., Psylliodes chrysocephusisispp sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psioloides , Agriotes spp.,

Conoderus spp., Melolontha melolontha, Amphimallon sόlstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.

From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp.,

Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tabanus spp. Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp ..

From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp .. " _^ ,

PCT / EP03 / 00051

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From the class of the Arachnida e.g. Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommodes spp., Ix. Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,

Hemitarsonemus spp., Brevipalpus spp ..

Plant-parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetians, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaph.

The substances according to the invention can be used with particularly good success for combating plant-damaging insects, such as e.g. against the larvae of the cucumber beetle (Diabrotica balteata), the caterpillars of the cotton capsule worm (Heliothis virescens), the larvae of the horseradish beetle (Phaedon cochleariae), the

Cabbage caterpillars (Plutella xylostella), army worm caterpillars (Spodoptera exigua and Spodoptera frugiperda), cotton aphid (Aphis gossypii) and peach aphid (Mycus persicae) or to control plant-damaging mites, such as against bean spanym mite (tica spica mite) ,

The substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.

Fungicides can be used to control Plasmodiophoromycetes,

Use Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides "can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae. Some pathogens of fungal and bacterial are exemplary but not limiting

Annotations that fall under the generic names listed above:

Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans; Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or

Pseudoperonospora cübensis; Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P. brassicae;

Erysiphe species, such as, for example, Erysiphe grarninis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P. grarninea

(Conidial form: Drechslera, Syn: Helminthosporium);

CochHobolus species, such as, for example, Cocbliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorurn;

Tilletia species, such as, for example, Tilletia caries; Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea; Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum; Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The active compounds according to the invention also have a strong strengthening effect

Plants on. They are therefore suitable for mobilizing the plant's own defenses against attack by unwanted microorganisms.

Plant-strengthening (resistance-inducing) substances are to be understood in the present context as those substances that are able to

To stimulate the defense system of plants so that the treated plants develop extensive resistance to these microorganisms when subsequently inoculated with unwanted microorganisms.

In the present case, undesirable microorganisms include phytopathogenic

Understand fungi, bacteria and viruses. The substances according to the invention can therefore be used to protect plants against attack by the named pathogens within a certain period of time after the treatment. The period within which protection is brought about generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

The active compounds according to the invention can be used with particularly good success to combat cereal diseases, such as mildew and rust, and against diseases in wine, fruit and vegetable cultivation, such as Venturia, Podosphaera and Sphaerothera species. The active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.

If appropriate, the active compounds according to the invention can also be used in certain concentrations and application rates as herbicides, for influencing plant growth, and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of further active compounds.

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and unwanted wild plants or crop plants (including naturally occurring crop plants). Cultivated 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 the plant cultivars which can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the customary treatment methods, for example by dipping, spraying, evaporating, atomizing, scattering, spreading and in the case of propagation material, in particular seeds single or multi-layer wrapping. In material protection, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.

In the present context, technical materials include non-living ones

Understand materials that have been prepared for use in the art. For example, technical materials that are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms , In the context of the materials to be protected, parts of production plants, for example cooling water circuits, are also mentioned which can be impaired by the multiplication of microorganisms. In the context of the present invention, the preferred technical materials are adhesives, glues, papers and cartons, leather, wood,

Paints, Kü lubricants and heat transfer liquids called, particularly preferably wood.

Bacteria, fungi, yeasts, algae and slime organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The active compounds according to the invention preferably act against fungi, in particular scummel fungi, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

For example, microorganisms of the following genera may be mentioned:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, like Chaetomium globosum,

Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum, " _^ ,

PCT / EP03 / 00051

- 23 -

Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus.

Depending on their respective physical and / or chemical properties, the active ingredients can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and also ULV cold and warm fog formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as Butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous triangular agents or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide. Possible solid carriers are: for example natural stone powders such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates.

Possible dispersants are: e.g. Lignin sulfite liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as Giimmiarabicum, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight

Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations, also in a mixture ^" with known fungicides, bactericides, acaricides, nematicides or insecticides, in order to broaden the spectrum of action or to prevent development of resistance, for example. In many cases, one obtains synergistic effects, ie the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

fungicides:

Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole,

azoxystrobin,

Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate,

buthiobate,

Calcium polysulfide, carpropamide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazon, chlorfenazol, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cyphofinililil, cymodinolanil, cymodinoxanil

Debacafb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dodipoxazolone, dodipoxazolone, dithipoxazol Ethirimol, etridiazole,

Famoxadone, Fenapanil, Fenarimol, Fenbuconazol, Fenfuram, Fenhexamid, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconazol, Flusamidolololol, Flusafilidololol, Flusafilidololol, Flurafilidolol, Flurililidolol, Flurafilidolol, Flurafilidolol, Flurililidolol, Flurililidolol, Flurililidolol, Flurafililolidol, Flusilanilolidol, Flurililidol, Flurililidol, Tolu, Flurililidol Folpet, Fosetyl-Alminium, Fosetyl-Sodium, Fthalide, Fuberidazole, Furalaxyl, Furametpyr, Furcarbonil, Furconazole,

Furconazole-cis, furmecyclox,

Guazatin, hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Immoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (D3P), Iprodione, Iprovahcarb, Irumamycin, Isoprothiolan, Isovaledione, Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Meferimzone, Mepampyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax,

Mildiomycin, Myclobutanil, Myclozolin, Nickel-dimethyldithiocarbamat, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin, Paclobutrazol, Pefurazoat, Penconuronolin, Polyconipolone, Phonocuronoxin, Phyconuronoxin, Pincurazoloxinoxin, Phonocuronoxin, Phonconazoloxinoxin Prochloraz, procymidone,

Propamocarb, propanosine sodium, propiconazole, propineb, pyraclostrobin, pyrazo- phos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinconazole, quintozen (PCNB), quinoxyfen, sulfur and sulfur preparations, spiroxarnine, tecloxazoletone, tebuconazoletone, tebuconazoletone Thiabendazole

Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, validamycin A, vinclozolin, Viniconazol, Zarilamid , Zineb, ziram as well

Dagger G, OK-8705, OK-8801, α- (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H-1, 2,4-triazole-1-ethanol, α- (2,4 -Dichlorophenyl) -ß-fluoro-ß-propyl-1 H-1, 2,4-τriazole-1-ethanol, α- (2,4-dichlorophenyl) -ß-methoxy-α-methyl-1H-1, 2 , 4-triazol-1-ethanol, α- (5-methyl-l, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] -lH-l, 2.4 triazole-1-ethanol,

(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-l, 2,4-triazol-l-yl) -3-octanone, (E) -α- (methoxyimino ) -N-methyl-2-phenoxy-ρhenylacetamide, l- (2,4-DicMorphenyl) -2- (lH-l, 2,4-triazol-l-yl) -e1hanon-O- (phenylmethyl) oxime, l- (2-methyl-l-naρhthalenyl) -lH-ρyrrol-2,5-dione, l- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-ρyrrolidinedione, 1 - [(Diiodomethyl) sulfonyl] -4-methyl-benzene, l - [[2- (2,4-dichlorophenyl) -l, 3-dioxolan-2-yl] methyl] -lH-imidazole, l- [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -lH-l, 2,4-triazole,

1 - [1 - [2- [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1 H-imidazole, 1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,

2 ^ 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-1rifluoromethyl-l, 3-thiazole-5-carboxanilide,

2,6-dichloro-5- (methylthio) -4-pyrimidinyl thiocyanate,

2,6-DicMor-N- (4-trifluoromethylbenzyl) benzamide, 2,6-Dicmor-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,

2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,

2 - [(1-methylethyl) sulfonyl] -5 - (trichloromethyl) - 1, 3, 4-thiadiazole,

2 - [[6-Deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -α-D-glucopyranosyl] -amino] -4- me1noxy-lH-pyrrolo [2,3-d] pyrirmdm-5-carbonitrile, 2-aminobutane,

2-bromo-2- (bromomethyl) -pentandinitril,

2-chloro-N- (2,3-dihydro-1,3,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamide,

2-CMOR-N- (2,6-dime1hylphenyl) -N- (isothiocyanatomethyl) -acetamide,

2-phenylphenol (OPP), 3,4-dichloro-l- [4- (difluoromethoxy) phenyl] -lH-pyrrole-2,5-dione,

3,5-dichloro-N- [cyan [(1-methyl-2-propynyl) -oxy] -methyl] -benzamide,

3- (1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,

3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] -pyridine,

4-CMor-2-cyan-N, N-dimethyl-5- (4-methylphenyl) - 1H-imidazole-1 -sulfonamide, 4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one .

8-hydroxyquinoline sulfate,

9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide, until _: (l-methylethyl) -3-methylyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate, cis-l- (4-chloropheyl) -2- (lH-l, 2,4-triazol-l-yl) cycloheptanol, cis-4- [3- [4- (l, l-dimethylpropyl) phenyl- 2-methylpropyl] -2,6-dimethyl-mo holin hydrochloride, " _^ ,

PCT / EP03 / 00051

- 28 -

Ethyl - [(4-chlorophenyl) azo] cyanoacetate,

Kaliiimhydrogencarbonat,

Methantetrathiol sodium salt,

Methyl l- (2,3-dihydro-2,2-dimethyl-lH-inden-l-yl) -lH-imidazole-5-carboxylate, methyl-N- (2 ₅ 6-dimethylphenyl) -N- (5 -isoxazolylcarbonyl) -DL-alaninate,

Methyl-N- (chlorace1l) -N- (2,6-dimethylphenyl) -DL-alaninate,

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetiahydro-2-oxo-3-furanyl) acetamide,

N- (2,6-dinιethylphenyl) -2-methoxy-N- (tetiahydro-2-oxo-3-t enyl) -acetarnide,

N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide, N- (4-cyclohexylphenyl) - 1, 4,5, 6-tetrahydro-2-pyrimidinamine,

N- (4-hexylphenyl) -l, 4,5,6-tetiahydro-2-pyrimidineamine;

N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidmyl) -acetamide,

N- (6-methoxy) -3-pyridmyl) -cycloproρancarboxamid,

N- [2,2,2-trichloro-l - [(chloroacetyl) aπιino] ethyl] benzamide, N- [3-chloro-4,5-bis (2-propmyloxy) phenyl] -N ' methoxy-methanimidamid,

N-formyl-N-hydroxy-DL-alanine sodium salt,

O, O-diethyl [2- (dipropylammo) -2-oxoethyl] -ethylphosphoranήdothioat,

O-methyl-S-phenyl-phenylpropylphosphoramidothioate,

S-methyl-l, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] -l-berιzopyran-2, i 3Η) -isobenzofuran] -3'-one,

4- [3,4-dimethoxyphenyl) -3- (4-fluorophenyl) acryloyl] -morpholirι

bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, Acephate, Acetamiprid, Acrmatiirin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin,

Azamethiphos, Azinphos A, Azinphos M, Azocyclotin, Bacillus popilliae, BaciUus sphaericus, BaciUus subtilis, BaciUus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Biofonifinin, Biethanifinin, Bioethanomifinin, Bioethanominomifin, Biomanoprofin , Butocarboxime, butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Chlovaporthrin, Chromafenozide, Cis-Resmethrin, Clofocentoprine Thrin, Clofocytophrine, Cofocenthrin, Cofocenthrin, Cofocenthrin , Cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,

Cypermetnrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Dicofol, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan,

Disulfoton, Docusat-sodium, Dofenapyn, 'Eflusilanate, Emamectin, Empentiirin, Endosulfan, Entomopfthora spp., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfös, Fenamiphos, Fenazatinothoximox, Fenazatinoxin, Fenazatinoxin, Fenazatinoxin fenoxycarb, fenpropathrin, fenpyrad, Fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazuron, Flubrocythrinate, flucycloxuron, Flucythrinate, flufenoxuron, flumethrin, Flutenzine, fluvalinate, fonophos, Fosmethilan, fosthiazate, Fub- fenprox, furathiocarb, granulosis

Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene, Imidacloprid, Indoxacarb, Isazofos, Isofenphos, Isoxathion, Ivermectin, Kernpolyederviruses, Lambda-cyhalothrin, Lufenuron

Malathion, Mecarbam, Metaldehyde, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathion, Methiocarb, Methoprene, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Milbemycin, Monöcrotophitites, Nylalramotnithine, Nine

Omethoate, Oxamyl, Oxydemethon M Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat,

Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A,

Pirimiphos M, Profenofos, Promecarb, Propargite, Propoxur, Prothiofos, Prothoat,

Pymetrozine, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridäben, Pyridathion, Pyrimidifen, Pyriproxyfen,

quinalphos,

ribavirin

Salithion, Sebufos, Silafluofen, Spinosad, Spirodiclofen, Sulfotep, Sulprofos,

Tau-fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Temivinphos, Terbufos, Tetrachlorvinphos, Tetradifon Theta- cypermethrin, Thiacloprid, Thiamethoxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxinoxinoxiloxiloxiloxinoxyloxiloxiloxinoxinoxiloxiloxinoxinoxiloxinoxiloxinoxiloxinoxinoxin

Triarathenes, triazamates, triazophos, triazuron, trichlophenidines, trichlorfon,

Triflumuron, Trimethacarb, Vamidothion, Vaniliprole, Verticillium lecanii

YI 5302

Zeta-cypermethrin, zolaprofos

(lR-cis) - [5- (phenylmethyl) -3-furanymethyl] -2,2-dimethylcyclopropanecarboxylate (3-phenoxyphenyl) methyl-2,2,3,3-tetramethylcyclopropane decarboxylate l - [(2-chloro-5 -tMazolyl) methyl] te1xahydro-3,5-dimethyl-N-mtro-l, 3,5-triazin-2 (1H) - imine

2- (2-chloro-6-fluorophenyl) -4- [4- (l ₅ l-dimethylethyl) phenyl] -4,5-dihydro-oxazole

2- (acetyloxy) -3-dodecyl-1,4-naphthalenedione 2-CMor-N - [[[4- (l-phenylethoxy) phenyl] aminino] carbonyl] benzamide

2-CUOR-N - [[[4- (2,2-dicMor-l, l-difluoroethoxy) -phenyl] -armno] carbonyl] -benzarnid

3-methylphenyl propyl carbamate

4- [4- (4-ethoxyphenyl) -4-methylpentyl] -l-fluoro-2-phenoxy-benzene

4-Cωor-2- (l, l-dimethylethyl) -5 - [[2- (2,6-d ^ 3 (2H) pyridazinone 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone

4-chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichlorophenyl) -3 (2H) -ρyridazinon

BaciUus thuringiensis strain EG-2348 benzoic acid [2-benzoyl-l- (l, l-dimethylethyl) hydrazide

Butanoic acid 2,2-dimethyl-3- (2,4-dichlorophenyl) -2-oxo-l-oxaspiro [4.5] dec-3-en-4-yl ester

[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidmylidene] 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-l-oxo-3-butenyl) -glycine

N- (4-Chlθhenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-

1-carboxamide

N - [(2-CMor-5-1rüazolyl) methyl] -N'-methyl-N '' - ni1xo-guanidine N-methyl-N '- (1-methyl-2-propenyl) - 1, 2-hydrazinedicarbothioamide

N-methyl-N'-2-propenyl-1, 2-hyά azmdicarbothioamide

O, O-Diethyl- [2- (dipropylam o) -2-oxoethyl] ethylphosphorarnidothioate

N-cyanomethyl-4-trifluorme1nyl-nicotinarnid

3,5-DicMor-1- (3,3-dicUor-2-propenyloxy) -4- [3- (5-1xifluoromethylpyridin-2-yloxy) propoxy] benzene

A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

In addition, the compounds of formula (I) according to the invention also have very good antifungal effects. They have a very broad antimycotic activity spectrum, especially against dermatophytes and fungi, mold and diphasic fungi (eg against Candida species such as Candida albicans, Candida glabrata) as well as Epidermophyton floccosum, Aspergillus species such as Aspergillus nigerumigatus and Aspergillus -Species such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audoüinii. The The list of these fungi does not in any way limit the mycotic spectrum that can be recorded, but is only of an explanatory nature.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.

When the active compounds according to the invention are used as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. When treating the soil, the active compound application rates are generally between 0.1 and

10,000 g / ha, preferably between 1 and 5,000 gΛia.

When used as insecticides, the active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.

The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active ingredient concentration of Application forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms.

When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.

As already mentioned above, all plants and their parts can be treated according to the invention. In a preferred embodiment, plant species and plant cultivars and their parts occurring wildly or obtained by conventional organic breeding methods, such as crossing or protoplast fusion, are treated. In a further preferred embodiment, transgenes are

Plants and plant varieties that have been obtained by genetic engineering methods, possibly in combination with conventional methods (Genetic Modified Organisms) and their parts treated. The term "parts" or "parts of plants" or "plant parts" was explained above.

Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with new properties (“traits”) which have been grown both by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, breeds, bio and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, nutrition), the treatment according to the invention can also give rise to superadditive ("synergistic") effects. For example, reduced application rates and / or extensions of the

W kimgsspektrum and / or an enhancement of the effect of the substances and agents usable according to the invention, better plant growth, increased tolerance against high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher harvest yields, higher quality and or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products possible, that go beyond the expected effects.

The preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which, by virtue of the genetic engineering modification, have received genetic material which gives these plants particularly advantageous, valuable properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated ripening, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products. Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses, and an increased tolerance of the plants to certain herbicidal active ingredients. Examples of transgenic plants are the important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes and cotton and rapeseed are highlighted. The traits are particularly emphasized as the increased defense of the plants against insects by toxins which arise in the plants, in particular those which are caused by the genetic material from BaciUus thuringiensis (for example by the genes CryIA (a), CryIA (b), CryIA (c), CryEA, CryEIA, CryEIB2 ₅ Cry9c Cry2Ab, Cry3Bb and CryTF as well as their combinations) are produced in the plants (hereinafter "Bt plants"). The increased resistance of plants against fungi, bacteria and viruses are also particularly emphasized as traits through systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. The traits that are particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example “P P-

Gene). The genes imparting the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are corn varieties, cotton varieties, soy varieties and potato varieties that are marketed under the trade names YTELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard®

(Cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are corn varieties, cotton varieties and soy varieties which are sold under the trade names Roundup Ready® (tolerance against glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance against phosphinotricin, e.g. rape), TMI® (tolerance against Imidazolinone) and STS®

(Tolerance to sulfonylureas e.g. maize). The herbicide-resistant plants (conventionally bred to herbicide tolerance) include the varieties sold under the name Clearfield® (e.g. maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").

The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.

The active compounds according to the invention act not only against plants, hygiene and

Pests, but also against the veterinary sector animal parasites (ectoparasites) such as tortoise ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, featherlings and fleas. These parasites include:

From the order of the Anoplurida e.g. Haematopinus spp., Linognathus spp.,

Pediculus spp., Phtirus spp., Solenopotes spp ..

From the order of the Mallophagida and the subordinates Amblycerina as well

Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp.,

Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp .. From the order Diptera and the subordinates Nematocerina as well

Brachycerina e.g. 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., Melophagus spp ..

From the order of the Siphonapterida e.g. Pulex spp., Ctenocephalides spp.,

Xenopsylla spp., Ceratophyllus spp .. From the order of the Heteropterida e.g. Cimex spp., Triatoma spp., Rhodnius spp.,

Panstrongylus spp ..

From the order of the Blattarida e.g. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp ..

From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata e.g. 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., Sternostoma spp., Varroa spp ..

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp. Tyfophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..

The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, house birds, aquarium fish and so-called experimental animals, such as Infest hamsters, guinea pigs, rats and mice. By fighting these arthropods, deaths and

Reductions in performance (for meat, milk, wool, skins, eggs, honey, etc.) are reduced, so that the use of the active compounds according to the invention enables more economical and simple animal husbandry.

The active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, for example by Injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or

Bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, powdering and with the help of shaped articles containing active ingredients, such as necklaces, ear tags, tail tags, limb tapes, holsters, marking devices, etc.

When used for cattle, poultry, pets, etc., the active compounds of the formula (T) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or apply after 100 to 10,000-fold dilution or use it as a chemical bath. " _^ ,

PCT / EP03 / 00051

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It has also been found that the compounds according to the invention have a high insecticidal action against insects which destroy industrial materials.

The following insects may be mentioned by way of example and preferably, but without limitation:

Beetle like

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Specus Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

Skin wings like

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites like

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.

Bristle tails such as Lepisma saccharina.

In the present context, technical materials include non-living ones

Understand materials such as preferably plastics, adhesives, glues, papers and cartons, leather, wood, wood processing products and paints.

The material to be protected against insect infestation is very particularly preferably wood and wood processing products. Wood and wood processing products, which can be protected by the agent according to the invention or mixtures containing it, are to be understood as examples:

Lumber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles,

Boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood, chipboard, carpentry or wood products that are used in general in house construction or joinery.

The active substances can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with at least one solution or

Diluent, emulsifier, dispersant and / or binder or fixative, water repellent, optionally siccatives and UV stabilizers and optionally dyes and pigments and other processing aids.

The insecticides used to protect wood and wood-based materials or

Concentrates contain the ^'active ingredient according to the invention in a concentration of 0.0001 to 95 wt .-%, in particular 0.001 to 60 wt .-%.

The amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.

An organic chemical solvent or solvent mixture and / or an oily or oily heavy serves as the solvent and / or diluent volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agent.

The organic chemical solvents used are preferably oily or oily ones

Solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, are used. Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.

Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C, turpentine oil and Like. Used.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C and / or locker oil and / or monochloronaphthalene, preferably - monochloronaphthalene, are used.

The organic non-volatile oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture. According to a preferred embodiment, part of the organic chemical solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture is replaced. Aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used.

In the context of the present invention, the known organic-chemical binders are water-thinnable and / or soluble or dispersible or emulsifiable in the organic-chemical solvents used

Synthetic resins and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, e.g. Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / / or synthetic resin used.

The synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.

According to the invention, at least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder. Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention. All or part of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

The plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glycerol glycerol or glycerol ether - Kolether, glycerol ester and p-toluenesulfonic acid ester.

Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.

Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.

A particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure process.

The ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.

The insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional admixing partners. The compounds mentioned in this document are an integral part of the present application.

Insecticides such as chlorpyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermetiirin, deltämethrin, Permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxide and triflumuron,

as well as fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanide, tolylfluanid,

3-iodo-2-propynyl butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octyl-isothiazolin-3-one.

At the same time, the compounds according to the invention can be used to protect objects, in particular hulls, sieves, nets, structures,

Quays and signaling systems that come into contact with sea or brackish water are used.

Overgrowth by sessile Ohgochaeten, such as Kallαöhrenworms and by mussels and species of the group Ledamorpha (barnacles), such as various Lepas and

Scalpellum species, or by species from the group Balanomorpha (barnacles), such as Baianus or Pollicipes species, increases the frictional resistance of ships and consequently leads to a significant increase in operating costs due to increased energy consumption and, moreover, frequent dry dock stays.

In addition to the growth by algae, for example Ectocarpus sp. and Ceramium sp., vegetation by sessile Entomostraken groups, which are grouped under the name Cirripedia (tendril crayfish), is particularly important.

It has now surprisingly been found that the compounds according to the invention, alone or in combination with other active ingredients, have an excellent antifouling effect.

By using compounds according to the invention alone or in combination with other active ingredients, the use of heavy metals, such as in bis- " _^ ,

PCT / EP03 / 00051

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(trialkyltin) sulfides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper (I) oxide, triethyltin chloride, tri-w-butyl (2-phenyl-4-chlorophenoxy) tin, tributyltin oxide, molybdenum disulfide, antimony oxide, polymeric butyl titanate, phenyl (bispyridine) bismuth chloride, tri - «- butyltin fluoride, manganese ethylene bisthiocarbamate, zinc dimethyl dithiocarbamate, zinc ethylene bisthiocarbamate, zinc and copper salts of 2-pyridine-thiol-1-oxy-oxychloride, bis (bisdimide) oxydimethylamide, bisdimide (bisdimide), bis (bisdimide), bis (bisdimide), bis (bisdimide) amide, bisdimide (bis) amdiboxamide, bis (bisdimide) amide, bis (bisbim) amide, bis (bisbim) amide, bis (bis) amdiboxamide -ethylene-bisdithiocarbamate, copper thiocyanate, copper phthalate and tri-butyltin halides or the concentration of these compounds can be significantly reduced.

The ready-to-use antifouling paints may also contain other active ingredients, preferably algicides, fungicides, herbicides, molluscicides or other antifouling active ingredients.

Suitable combination partners for the anti-fouling agents according to the invention are preferably:

Algicides like

2-tert-butylarrώ o-4-cyclopropylarn o-6-m dichlorophen, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen,

Quinoclamine and Terbutryn;

Fungicides like

Benzo [&] thiophenecarboxylic acid cyclohexylamide-S, S-dioxide, dichlofluanide, fluorofolpet, 3-iodo-2-propynyl butyl carbamate, tolyl fluanide and azoles such as

Azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and tebuconazole;

Molluscicides such as fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb; or conventional antifouling agents such as

4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulfone, 2- (N, N-dimethyl1niocarbamoylthio) -5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinethiol -l-oxide, pyridine-triphenylborane, teträbutyldistannoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,5, 6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4,6-trichlorophenylmaleimide ,

The antifouling agents used contain the active compound according to the invention of the compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular of 0.01 to 20% by weight.

The antifouling agents according to the invention furthermore contain the usual constituents, e.g. in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

In addition to the algicidal, fungicidal, molluscicidal and insecticidal active compounds according to the invention, antifouling paints contain in particular binders.

Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in one

Solvent system in particular in an aqueous system, vinyl chloride / vinyl acetate copolymer systems. In the form of aqueous dispersions or in the form of organic solvent systems, butadene / styrene acrylonitrile rubbers, drying oils, such as linseed oil, resin esters or modified hard resins in combination with tar or bitumen , Asphalt and epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.

Paints may also contain inorganic pigments, organic

Pigments or dyes, which are preferably insoluble in sea water. Paints may also contain materials such as rosin in order to be controlled

To enable release of the active ingredients. The paints can also Plasticizers containing modifiers affecting theological properties and other conventional ingredients. The compounds according to the invention or the abovementioned mixtures can also be incorporated into self-polishing antifouling systems. -

The active ingredients are also suitable for controlling animal pests, in particular insects, arachnids and mites, which live in closed spaces such as apartments, factory halls, offices, vehicle cabins, etc. occurrence. To control these pests, they can be used alone or in combination with other active ingredients and auxiliaries in household insecticide products.

They are effective against sensitive and resistant species and against all stages of development. These pests include:

From the order of the Scorpionidea e.g. Buthus occitanus. From the order of the Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp.,

Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat,

Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis,

Dermatophagoides pteronissimus, Dermatophagoides forinae.

From the order of the Araneae e.g. Aviculariidae, Araneidae. From the order of the Opiliones e.g. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda e.g. Oniscus asellus, Porcellio scäber.

From the order of the Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp ..

From the order of the Chilopoda e.g. Geophüus spp .. From the order of the Zygentoma e.g. Ctenolepisma spp., Lepisma saccharina,

Lepismodes inquilinus.

From the order of the Blattaria e.g. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

From the order of the Saltatoria, for example Acheta domesticus. From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera e.g. Kalotermes spp., Reticulitermes spp.

From the order of the Psocoptera e.g. Lepinatus spp., Liposcelis spp.

From the order of the Coleptera e.g. Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera e.g. Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis,

Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.

From the order of the Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.

From the order of the Siphonaptera e.g. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.

From the order of the Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.

From the order of the anoplura e.g. Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pübis.

From the order of the Heteroptera e.g. Cimex hemiptems, Ci ex lectularius,

Rhodinus prolixus, Triatoma infestans.

The application in the field of household insecticides is carried out alone or in combination with other suitable active ingredients such as phosphoric acid esters, carbamates,

Pyrethroids, growth regulators or active substances from other known classes of insecticides.

They are used in aerosols, unpressurized sprays, e.g. pump and atomizer sprays, automatic fog machines, foggers, foams, gels, evaporator products with evaporator plates made of cellulose or plastic, liquid evaporators, Gel and membrane evaporators, propeller-driven evaporators, energy-free or passive evaporation systems, moth papers, moth bags and moth gels, as granules or dusts, in lures or bait stations.

The preparation and use of the substances according to the invention can be seen from the following examples.

Herstelhmgsbeispiele

example 1

(Procedure a / variant 1)

To a solution of 3.2 g (0.0123 mol) of 4- (2-tert-butyl-tetrazol-5-yl) phenyl acetic acid in 80 ml of methylene chloride is added 1.6 g (0.0137 Mol) thionyl chloride. The mixture is then boiled under reflux until the evolution of gas has ended, the solvent is distilled off in vacuo and the residue is dissolved in 50 ml of methylene chloride. With cooling, this solution is added at 0 ° C. to a solution of 1.9 g (0.0123 mol) of 2-elnyl-3-cωor-4-ammopyridine and 1.4 g (0.014 mol) of triethylamine in 50 ml of methylene chloride. The reaction mixture is stirred for 16 hours at room temperature, then evaporated in vacuo and the residue is shaken with ethyl acetate and water. The organic phase is dried over sodium sulfate and evaporated in vacuo. The residue is purified by silica gel chromatography (methylene chloride / methanol 7: 1).

This gives 0.9 (18% of theory) of 4- (2-tert-butyl-tetrazol-5-yl) phenylacetic acid-N-

(2-ethyl-3-chloro-pyrid-4-yl) amide in the form of a colorless solid with the logP (pH2) = 2.34.

A mixture of 6.9 g (0.034 mol) of 4- (tetrazol-5-yl) phenylacetic acid, 75 ml of trifluoroacetic acid, 14.8 g (0.2 mol) of tert-butanol and 1.85 ml of conc. Sulfuric acid is stirred for 16 hours at room temperature. Then the reaction mixture is evaporated in vacuo and the residue is shaken with ethyl acetate and water. The organic phase is dried over sodium sulfate and evaporated in vacuo. The residue is purified by silica gel chromatography (methylene chloride / diethyl ether 1: 1).

5.74 g (65% of theory) of an4- (2-tert-butyl-tetrazol-5-yl) -phenylacetic acid are thus obtained in the form of colorless crystals with the logP (ρH2) = 2.18.

Production of the VorrjrojMξtes

A mixture of 12.8 g (0.08 mol) of 4-cyanophenylacetic acid, 11 g (0.17 mol)

Sodium azide, 23.4 g (0.17 mol) of triethylamine hydrochloride and 150 ml of toluene are boiled under reflux for 16 hours. The mixture is then cooled to room temperature, the organic phase is decanted and 100 ml of 5% sodium hydroxide solution are added to the oily residue. The solution is then filtered through Celite and the filtrate is acidified with dilute hydrochloric acid. The precipitated product is suctioned off and washed with water. _n , "

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This gives 10 g (62% of theory) of 4- (tetrazol-5-yl) phenylacetic acid as a beige powder with the logP (pH2) = 0.61.

Example 2

(Method a / variant 2) To a solution of 1.5 g (6.6 mmol) of 4- (4-cyano-pyrazol-l-yl) -phenylacetic acid in

50 ml of dioxane are added at 5-10 ° C 1.3 g (0.06 mol) of N \ N'-carbonyl-diimidazole and the mixture is stirred at 10 ° C for 1 hour. Then 7.4 g (0.045 mol) of 2-ethyl-3-cMor-4-aminopyridine are added in portions and the mixture is boiled under reflux for 18 hours. The solvent is then evaporated off in vacuo and the residue is shaken with ethyl acetate and water. The organic phase is dried over sodium sulfate and evaporated in vacuo. The residue is purified by silica gel chromatography.

This gives 0.1 g (4% of theory) of 4- (4-cyano-pyrazol-l-yl) phenylacetic acid N- (2-ethyl-3-chloropyrid-4-yl) - amide in the form of beige crystals with the logP (pH2) = 1.60.

A mixture of 40 g (0.066 mol) of 4-hydrazinophenylacetic acid hydrochloride in 400 ml of ethanol is mixed with 12 g (0.073 mol) of 2-hydroxymethylene-3,3-dimethoxy-propionitrile sodium salt (preparation see EP 279 556) and stirred for 16 hours at room temperature. The mixture is then refluxed for 2 hours and then evaporated in vacuo. The residue is triturated with water and then the precipitated product is suctioned off.

13.1 g (87% of theory) of 4- (4-cyano-pyrazol-l-yl) phenylacetic acid are thus obtained in the form of a beige powder with the logP (pH2) = 1.46.

Example 3

(Method b)

To a solution of 1 g (2.5 mmol) of 4- (4,4,5,5, tetramethyl-l, 3,2-dioxaborolan-2-yl) phenylacetic acid-N- (2-ethyl-3-chloro) pyrid-4-yl) -amide and 0.7 g (3 mmol) of 2-methoxy-5-bromopyridine in 60 ml of 1,2-dimethoxyethane are added under an argon atmosphere 0.1 g of 1,1 '- [bis- (Diphenylphospl ιo) -ferrocene] -dichloropalladium-DicMormethane complex and 5 ml of 2M sodium carbonate solution. The mixture is stirred at 80 ° C for 16 hours. The reaction mixture is then filtered through Celite and the filtrate is evaporated in vacuo. The residue is purified by silica gel chromatography (methylene chloride / ethyl acetate 1: 1). " _^ ,

PCT / EP03 / 00051

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0.7 g (73% of theory) of 4- (2-methoxy-pyrid-5-yl) phenylacetic acid-N- (2-ethyl-3-chloropyrid-4-yl) are thus obtained. amide with the logP (pH2) = 2.05.

To a solution of 7 g (0.02 mol) of 4-bromophenylacetic acid-N- (2-ethyl-3-chloropyrid-4-yl) -amide in 150 ml of dioxane, 5.9 g (0.05 06 mol) potassium acetate, 5.5 g (0.022 mol) bis- (pinacolato) diborane, 0.4 gl, l '- [bis- (diphenylphosphmo) -feιrocen] -dichlorpalladiiLm-DicUormethane complex and 0.3 g 1 , 1 '-Bis- (diphenyl-phosphino) ferrocene and the mixture is stirred for 21 hours at 80 ° C. Then the reaction mixture is poured onto water and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and evaporated in vacuo. The residue is triturated with disiopropyl ether and the precipitated product is filtered off with suction.

4.8 g (60% of theory) of 4- (4,4,5,5-tetramethyl-l, 3,2-dioxaborolan-2-yl) phenylacetic acid N- (2-ethyl- 3-chloro-pyrid-4-yl) amide in the form of colorless crystals with the logP (pH2) = 2.69. Production of the Vgrrjr product

9.7 g (0.06 mol) of N ', N'-carbonyldiimidazole are added to a solution of 10.8 g (0.05 mol) of 4-bromophenylacetic acid in 100 ml of dioxane at room temperature and the mixture is stirred Mix after 1 hour at room temperature. 7.4 g ((0.045 mol)) of 2-ethyl-3-chloro-4-aminopyridine are then added in portions and the mixture is refluxed for 1 hour, after which the solvent is evaporated off in vacuo and the residue is shaken with ethyl acetate and water. The organic phase is dried over sodium sulfate and evaporated in vacuo, and the residue is recrystallized from acetonitrile.

5.9 g (35% of theory) of 4-bromophenylacetic acid-N- (2-ethyl-3-chloropyrid-4-yl) -amide are thus obtained in the form of beige crystals with the logP (pH2) = 2.09.

The compounds of the formula (Ia) given in Table 1 below are obtained analogously to Examples 1 to 3 or according to the general information on the preparation: Table 1

The logP values specified in the tables and manufacturing examples above are determined in accordance with EEC Directive 79/831 Annex V.48 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (CI 8). Temperature: 43 ° C.

The determination is carried out in the acidic range at pH 2.3 with 0.1% aqueous phosphoric acid and acetonitrile as eluents; linear gradient from 10% acetonitrile to 90% acetonitrile.

The calibration is carried out with unbranched alkan-4-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values on the basis of the retention time by linear interpolation between two successive alkanones).

applications

Example X

Aphis gossypii test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

For the production ^'of a suitable preparation of active mixed, 1 part by weight of active compound with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Cotton leaves (Gossypium hirsutum), which are heavily infested with the cotton aphid (Aphis gossypii), are treated by immersing them in the active ingredient preparation of the desired concentration.

After the desired time, the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.

In this test, at an exemplary active ingredient concentration of 500 ppm, e.g. compound 1 of the production examples a killing of 100% and compound 20 of the production examples a killing of 95%, in each case after 6

Days. 03 00051

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Example B

Diabrotica test (larvae in the soil)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts 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 to the desired amount with water containing emulsifier

Concentration.

Pots filled with soil are poured into the active ingredient preparation. Immediately after the preparation, 5 corn kernels are laid out per pot and after 3 days the Diabrotica balteata larvae are placed on the treated soil. The concentration given relates to the amount of active ingredient per unit volume of soil (mg / 1).

After the desired time, the accumulated maize plants are counted and the efficiency is calculated. 100% means that all maize plants have emerged; 0% means that no maize plants have emerged.

In this test, at an exemplary active ingredient concentration of 500 ppm, compound 1 of the preparation examples, for example, shows a kill of 100% after 10 days. Example C

Heliothis virescens test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2. Parts 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 to the desired amount with water containing emulsifier

Concentration.

Soybean shoots (Glycine max) are treated by dipping into the active ingredient preparation of the desired concentration and populated with Heliothis virescens caterpillars while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

In this test, at an exemplary active ingredient concentration of 500 ppm, compound 7 of the preparation examples, for example, shows a kill of 100% after 7 days.

T EP03 / 00051

62

Example D

Meloidogyne Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts 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.

Vessels are filled with sand, active ingredient solution, Meloidogyne incognita egg larva suspension and lettuce seeds. The lettuce seeds germinate and the plantlets develop. The galls develop at the roots.

After the desired time, the nematicidal effect is determined in% using the formation of bile. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.

In this test, at an exemplary active ingredient concentration of 500 ppm, the compounds 1, 2, 3, 6, 7, 8, 9, 10, 11, 12, 13, 21, 22, 24, 25, 26, 27, 29, 31, 35 and 37 of the production examples after 100 days a 100% kill.

" _^ ,

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Example E

Myzus test (systemic effect)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts 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 to the desired amount with water containing emulsifier

Concentration.

Savoy cabbage plants (Brassica oleracea), which are heavily infested with the green peach aphid (Myzus persicae), are watered with 10 ml active ingredient preparation of the desired concentration, so that the active ingredient preparation in the

Soil penetrates without wetting the sprout. The active ingredient is absorbed by the roots and passed on to the shoot.

After the desired time, the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.

In this test, at an exemplary active ingredient concentration of 500 ppm, e.g. Compounds 1, 11, 27 and 36 of the preparation examples have a kill rate of 95%, compounds 24 and 32 of the production examples have a kill rate of 98%

% and compound 34 of the preparation examples killed 99%, in each case after 6 days. Example F

Phaedon larvae test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts 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 to the desired amount with water containing emulsifier

Concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the horseradish leaf beetle (Phaedon cochleariae) while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.

In this test, at an exemplary active ingredient concentration of 500 ppm, the compounds 1, 2, 3, 6, 7, 8, 9, 10, 11, 12, 13, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 31, 32, 33, 34, 35, 36 and 37 of the production examples after 100 days a 100% kill. Example G

Plutella Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts 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 to the desired amount with water containing emulsifier

Concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the cockroach (Plutella xylostella) while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

In this test, at an exemplary active ingredient concentration of 500 ppm, compound 7 of the preparation examples, for example, shows a kill of 100% after 7 days.

Example H

Spodoptera exigua test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts 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 to the desired amount with water containing emulsifier

Concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active ingredient of the desired concentration and populated with caterpillars of the army worm (Spodoptera exigua) while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

In this test, at an exemplary active ingredient concentration of 500 ppm, compound 7 of the preparation examples, for example, shows a kill of 100% after 7 days.

Example I

Spodoptera frugiperda test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts 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 to the desired amount with water containing emulsifier

Concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the army worm (Spodoptera frugiperda) while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

In this test, at an exemplary active ingredient concentration of 500 ppm, the compounds 1, 2, 3, 5, 6, 7, 8, 9, 10, 11, 19, 20, 21, 23, 24, 25, 26, 27, 29, 31, 34, 35, 36 and 37 of the manufacturing examples after 100 days a 100% kill. Example J

Tetranychus test (OP-resistant / immersion treatment)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts 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 to the desired amount with water containing emulsifier

Concentration.

Bean plants (Phaseolus vulgaris), which are heavily infested with all stages of the common spider gullet (Tetranychus urticae), are immersed in an active ingredient preparation of the desired concentration.

After the desired time, the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.

In this test, at an exemplary active substance concentration of 100 ppm, for example, compound 19 of the preparation examples shows 95% kill and compound 34 of the preparation examples shows 100% kill, in each case after 7 days.

0051

- 69 -

Example K

Heliothis virescens - test (treatment of transgenic plants)

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 amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired level

Concentration.

Soybean shoots (Glycine max) of the Roundup Ready variety (trademark of Monsanto Comp. USA) are treated by dipping into the preparation of active compound of the desired concentration and are populated with the tobacco bud caterpillar Heliothis virescens while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

Example L

Diabrotica balteata test (larvae in the soil)

Limit concentration test / soil insects - treatment of transgenic plants

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 amount of solvent, the specified amount is given

Amount of emulsifier and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is poured onto the floor. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (mg / 1). You fill the bottom in 0.25 1 pots and let them stand at 20 ° C.

Immediately after the preparation, 5 pre-germinated maize kernels of the YTELD variety are added to each pot

GUARD (trademark of Monsanto Comp., USA). After 2 days, the appropriate test insects are placed in the treated soil. After a further 7 days, the effectiveness of the active ingredient is determined by counting the maize plants that have emerged (1 plant = 20% activity). Example M

Podosphaera test (apple) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide emulsifier: 1.0 part by weight of alkyl aryl 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.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of the Podosphaera leucotricha apple flour thawing agent. The plants are then placed in the greenhouse at about 23 ° C. and a relative humidity of about 70%.

Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, at an exemplary application rate of 100 g / ha, the compounds 3, 9, 11, 13, 24, 26, 31, 32 and 34 of the preparation examples, for example, show an efficiency of at least 98%. Example N

Venturia test (apple) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide emulsifier: 1.0 part by weight of alkyl aryl 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.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous comedy suspension of the Venturia inaequalis apple scab pathogen and then remain in an incubation cabin at about 20 ° C. and 100% relative atmospheric humidity for 1 day.

The plants are then placed in the greenhouse at approx. 21 ° C. and a relative humidity of approx. 90%.

Evaluation is carried out 10 days after the inoculation. 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, at an exemplary application rate of 100 g / ha, the compounds 3, 9, 11, 13, 24, 26, 31, 32 and 34 of the preparation examples, for example, show an efficiency of at least 85%. Example O

Sphaerotheca test (cucumber) / protective

Solvent: 49 parts by weight of N, N-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.

To test for protective effectiveness, young cucumber plants are sprayed with the preparation of active compound in the stated application rate. 1 day after the treatment, the plants are inoculated with a spore suspension of Sphaerotheca fuliginea. The plants are then placed in a greenhouse at 70% relative atmospheric humidity and a temperature of 23 ° C.

Evaluation is carried out 7 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, at an application rate of 750 g / ha, for example, compounds 6, 9, 13 and 21 of the preparation examples show an efficiency of 100%. Example P

Puccinia test (wheat) / protective

Solvent: 25 parts by weight of N, N-dimethylacetamide

Emulsifier: 0.6 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.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Puccinia recondita. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours.

The plants are then placed in a greenhouse at a temperature of approximately 20.degree. C. and a relative atmospheric humidity of 80% in order to promote the development of rust pustules.

Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, with an exemplary application rate of 500 g / ha, e.g. the compounds 1 and 3 of the preparation examples have an efficiency of 100%.

Claims

claims

Substituted 4-aminopyridine derivatives of the formula (I)

in which

R ^{1 represents} alkyl,

R ^{2 represents} halogen,

Het represents an optionally substituted heterocycle,

n represents 1 or 2,

Y stands for halogen, alkyl or haloalkyl and p stands for 0, 1 or 2.

Substituted 4-aminopyridine derivatives of the formula (I) according to Claim 1, in which

R ^{1 represents} CC ₄ alkyl,

R ^{2 represents} fluorine, chlorine, bromine or iodine,

Het for an optionally mono- or polysubstituted, identically or differently substituted 5- or 6-membered heterocycle having 1 to 4 heteroatoms, such as N, O or S, examples of which may be mentioned as substituents:

Halbgen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, cyano, nitro, formyl, hyfooxyimino, alkoxyimino, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl; gegebe- optionally substituted phenyl, optionally substituted morpholino or optionally substituted tetrazolyl,

n represents 1 or 2,

Y for fluorine, chlorine, bromine; d- alkyl or d- haloalkyl, p represents 0, 1 or 2.

Substituted 4-aminopyridine derivatives of the formula (I) according to Claim 1, in which

R ^{1 represents} Cr _∑ alkyl,

R ^{2 represents} fluorine, chlorine or bromine,

Het for 5- or 6-membered heterocycles from the series of thienyl, oxazolyl, isoxazolyl, pyrazolyl; 1,2,4-oxadiazolyl; 1,2,4-thiadiazolyl; 1,3,4-thiadiazolyl; Tetrazolyl, pyridinyl, pyrimidinyl or pyridonyl, each of which can be substituted one to three times (depending on the respective substitution options), identically or differently, examples of which may be mentioned as substituents: fluorine, chlorine, bromine, iodine; C ₁ -C ₄ alkyl; C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio; in each case one to five times, identical or different, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy and C ₁ -C -alkylthio substituted by fluorine or chlorine; Cyano, nitro, formyl, hydroxyimino, - -alkoxyimino, -C-C ₄ - alkylcarbonyl, Ci-C ^ alkoxycarbonyl, C ₁ -C -alkoxycarbonyl-C ₁ -C - alkyl; phenyl optionally substituted to triple, identically or differently, by fluorine, chlorine, bromine, -Gralkyl, C ₁ -C ₄ haloalkyl, alkoxy, C ₁ -C ₄ haloalkoxy, nitro or cyano; optionally morpholino which is monosubstituted to triple, identical or different, substituted by fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl or tetrazolyl which is optionally substituted by CrC ₄ -alkyl, n represents 1 or 2,

Y represents fluorine, chlorine, methyl or trifluoromethyl, p represents 0, 1 or 2.

Substituted 4-aminopyridine derivatives of the formula (I) according to spoke 1, in which

R ^{1 represents} ethyl, R ^{2 represents} chlorine,

Het for 5- or 6-membered heterocycles from the series of thienyl, oxazolyl, isoxazolyl, pyrazolyl; 1,2,4-oxadiazolyl; 1,2,4-thiadiazolyl; 1,3,4-thiadiazolyl; Tetrazolyl, pyridinyl, pyrimidinyl or pyridonyl, each of which can be substituted one to three times (depending on the respective substitution options), identically or differently, examples of which may be mentioned as substituents: fluorine, chlorine, bromine; Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl; Methoxy, ethoxy, n- or i-propoxy; Methylthio, ethylthio, n- or i-propylthio; Trifluoromethyl, difluoromethyl, fluoromethyl; Trifluoromethoxy, difluoromethoxy; trifluoromethylthio; Cyano, formyl,

Hydroximino, methoxyimino, ethoxyimino; Methylcarbonyl, ethylcarbonyl; Methoxycarbonyl, ethoxycarbonyl; Methoxycarbonyl-methyl, 1-methoxycarbonyl-1-ethyl; phenyl optionally substituted one to two times, identically or differently, by fluorine, chlorine, methyl, methoxy, trifluoromethyl, nitro or cyano; optionally morpholino substituted once or twice, identically or differently by fluorine, chlorine, methyl or ethyl, or optionally substituted by tetrazolyl substituted by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,

n represents 1 or 2, p stands for 0.

Process for the preparation of substituted 4-aminopyridine derivatives of the formula (I) according to Claim 1, characterized in that

a) 4-aminopyridines of the formula (TT)

in which

R and R have the meanings given in Claim 1,

and phenylacetic acids of the formula (ET)

in which

Het, Y, n and p have the meanings given in Claim 1,

(1) reacted with a halogenating agent, preferably thionyl chloride, optionally in the presence of an acid binding agent and optionally in the presence of a diluent; or

(2) in the presence of a catalyst activating the carboxyl group and in the presence of a diluent; or b) substituted 4-aminopyridines of the formula (IV)

in which

R ¹ and R ^{2 have} the meanings given in spoke 1 and

Q represents a leaving group,

with bromides of the formula (V)

in which

Het, Y and p have the meanings given in spoke 1 and m represents 0 or 1,

in the presence of a base, in the presence of a catalyst and in

In the presence of a diluent; or

c) substituted 4-aminopyridines of the formula (VT)

in which

R ¹ and R ^{2 have} the meanings given in Claim 1, with compounds of the formula (VE)

in which

Het, Y and p have the meanings given in spoke 1, Q and m have the meanings given above,

in the presence of a base, in the presence of a catalyst and in the presence of a diluent.

6. Agents for controlling pests and or undesirable microorganisms, characterized by a content of at least one compound of the formula (I) according to spoke 1 in addition to extenders and / or surface-active substances.

7. Use of compounds of the formula (I) according to spoke 1 for combating pests and / or unwanted microorganisms.

8. A method for controlling pests and / or undesirable microorganisms, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or microorganisms and / or their respective habitat.

9. A process for the preparation of agents for controlling pests and / or undesirable microorganisms, characterized in that compounds of the formula (I) according to spoke 1 are mixed with extenders and / or surface-active substances. Phenylacetic acids of the formula (ET)

in which

Het, Y, n and p have the meanings given in spoke 1.

Substituted 4-aminopyridines of the formula (TV)

in which

R ¹ and R ^{2 have} the meanings given in spoke 1 and

Q stands for an exit group.