DE10201764A1 - Substituted 4-aminopyridine derivatives - Google Patents

Abstract

New substituted 4-aminopyridine derivatives of the formula (I) DOLLAR F1 in which DOLLAR AR · 1 ·, R · 2 ·, Het, n, Y and p have the meanings given in the description, DOLLAR A several processes for the preparation of these substances and their use for controlling pests, and new intermediates and processes for their production.

Description

The present invention relates to new substituted 4-aminopyridine derivatives, Process for their preparation and their use as Pesticides and to combat unwanted microorganisms.

It is already known that certain substituted 4-aminopyridines are insecticidal Have properties (cf. e.g. WO 93/04580, WO 96/08475, WO 96/10016 or WO 96/33975). The effectiveness or range of action of these compounds is however, especially not at low application rates and concentrations always fully satisfactory.

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

• a) 4-Aminopyridine der Formel (II)
  
  
  in welcher
  R¹ und R² die oben angegebenen Bedeutungen haben,
  und Phenylessigsäuren der Formel (III)
  
  
  in welcher
  Het, Y, n und p die oben angegebenen Bedeutungen haben,
  • 1. mit einem Halogenierungsmittel, vorzugsweise Thionylchlorid, gegebenenfalls in Gegenwart eines Säurebindungsmittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt; oder
  • 2. in Gegenwart eines die Carboxyl-Gruppe aktivierenden Katalysators und in Gegenwart eines Verdünnungsmittels umsetzt;

oder

• a) substituierte 4-Aminopyridine der Formel (IV)
  
  
  in welcher
  R¹ und R² die oben angegebenen Bedeutungen haben und
  Q für eine Abgangsgruppe steht,
  mit Bromiden der Formel (V)
  
  
  in welcher
  Het, Y und p die oben angegebenen Bedeutungen haben und
  m für 0 oder 1 steht,
  in Gegenwart einer Base, in Gegenwart eines Katalysators und in Gegenwart eines Verdünnungsmittels umsetzt;

oder

• a) substituierte 4-Aminopyridine der Formel (VI)
  
  
  in welcher
  R¹ und R² die oben angegebenen Bedeutungen haben,
  mit Verbindungen der Formel (VII)
  
  
  in welcher
  Het, Q, Y, m und p die oben angegebenen Bedeutungen haben,
  in Gegenwart einer Base, in Gegenwart eines Katalysators und in Gegenwart eines Verdünnungsmittels umsetzt.

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

• a) 4-aminopyridines of the formula (II)
  
  
  in which
  R ¹ and R ^{2 have} the meanings given above,
  and phenylacetic acids of the formula (III)
  
  
  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 catalyst activating the carboxyl group and in the presence of a diluent;

or

• a) substituted 4-aminopyridines of the formula (IV)
  
  
  in which
  R ¹ and R ^{2 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

• a) substituted 4-aminopyridines of the formula (VI)
  
  
  in which
  R ¹ and R ^{2 have} the meanings given above,
  with compounds of the formula (VII)
  
  
  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 pronounced biological properties and above all to control animal pests, especially insects, Arachnids and nematodes, which are used in agriculture, in forests, in stock and Material protection as well as in the hygiene sector, as well as to combat of undesirable microorganisms are suitable.

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

Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below:
R ¹ preferably represents C ₁ -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, alkoxyimino, 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 C ₁ -C ₄ haloalkyl,
p is preferably 0, 1 or 2.
R ¹ particularly preferably represents 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-thiadiazolyl; 1,3,4-thiadiazolyl; Tetrazolyl, pyridinyl, pyrimidinyl or pyridonyl, which can each be monosubstituted to trisubstituted (depending on the respective substitution options), may be substituted 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; each C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ alkylthio which are mono- to quintuple, identical or different, substituted by fluorine or chlorine; Cyano, nitro, formyl, hydroxyimino, C ₁ -C ₄ alkoxyimino, C ₁ -C ₄ alkylcarbonyl, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkoxycarbonyl-C ₁ -C ₄ alkyl; phenyl optionally substituted 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; optionally single to triple, identical or different, fluorine, chlorine, bromine or C ₁ -C ₄ alkyl substituted morpholino or optionally substituted by C ₁ -C ₄ 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, which can in each case be substituted 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 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 methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl tetrazolyl.
n very particularly preferably represents 1 or 2.
p very particularly preferably stands for 0.

The above-mentioned radical definitions can be used with each other in any way be combined. In addition, individual definitions can also be omitted.

The residue definitions listed in the above and below are Carbon residues, such as alkyl - also in connection with heteroatoms, such as alkoxy - to the extent possible, straight or branched.

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

If, for example, 4- (4-cyano-pyrazol-1-yl) phenylacetic acid and 2-ethyl-3-chloro-4-aminopyridine are used as starting materials and N, N-carbonyl-bisimidazole is used as the catalyst, the course of the reaction of the process according to the invention can be carried out (a, variant 2) can be represented by the following formula:

For example, 4- (4,4,5,5-tetramethyl-1,3,2-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-chloro-pyridin-4-yl) amide and 2-methoxy-pyridin-5-yl-boronic acid are used as starting materials, the reaction sequence of the process according to the invention can (c) are represented by the following formula scheme:

Formula (II) provides a general definition of the 4-aminopyridines to be used as starting materials for carrying out process (a) according to the invention. In this formula, R ¹ and R ^{2 are} preferably, particularly preferably or very particularly preferably 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 called.

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

In addition, in process (a) according to the invention as starting materials Phenylacetic acids using are generally defined by the formula (III). In In this formula, Het, n, Y and p are preferred, particularly preferred or entirely particularly preferred for those meanings that are already in connection with the Description of the compounds of formula (I) according to the invention for these radicals have been mentioned as preferred, particularly preferred or very particularly preferred.

The phenylacetic acids of formula (III) are new and also the subject of this Registration. They are obtained by looking at the heterocyclic residue in known Builds up on the appropriately substituted phenyl.

So z. B. the 4-tetrazolylphenylacetic acids obtained by 4-cyanophenylacetic acid with sodium azide in the presence of an amine hydrochloride (e.g. Ammonium chloride or trialkylammonium chloride) and in the presence of an inert organic solvent (e.g. toluene) at temperatures between 50 ° C and 150 ° C, preferably between 80 ° C and 120 ° C (see also the Preparation Examples). The tetrazolyl residue can then still in the usual way are alkylated (see also the preparation examples).

The 4-pyrazolylphenylacetic acids are e.g. B. obtained by 4-hydrazinophenylacetic acid hydrochloride with sodium salts of 2-substituted 1-hydroxy 3,3-dimethoxy-1-propene derivatives in the presence of an inert organic Solvents, such as ethanol, at temperatures between 20 ° C and 50 ° C implemented (see also the manufacturing examples).

Formula (IV) provides a general definition of the substituted 4-aminopyridines to be used as starting materials for carrying out process (b) according to the invention. In this formula, R ¹ and R ^{2 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) ₂ ; 4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl; 5,5-dimethyl-1,3,2-dioxo-borinan-2-yl; 4,4,6-trimethyl-1,3,2-dioxo-borinan-2-yl or 1,3,2-benzodioxoborolan-2-yl.

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


in which
R ¹ and R ^{2 have} the meanings given above,
with 4-bromophenylacetic acid of the formula (VIII)


in accordance with the conditions of process (a) and the substituted 4-aminopyridines of the formula (VI) thus obtained


in which
R ¹ and R ^{2 have} the meanings given above,
with known boron derivatives of the formula (IX)

HQ (IX)

in which
Q has the meanings given above,
implemented according to the conditions of process (c) (see also the production examples).

Which also as starting materials in process (b) according to the invention Bromides using are generally defined by formula (V). In this formula Het, Y and p are preferred, particularly preferred or very particularly preferred for those meanings already related to the description of the Compounds of the formula (I) according to the invention are preferred for these radicals, were particularly preferred or very particularly preferred. m stands preferably for 0 or 1.

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

Formula (VI) provides a general definition of the substituted 4-aminopyridines to be used as starting materials for carrying out process (c) according to the invention. In this formula, R ¹ and R ^{2 are} preferably, particularly preferably or very particularly preferably 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 called.

The substituted 4-aminopyridines of formula (VI) are obtained by using 4- Aminopyridines of formula (II) with 4-bromophenylacetic acid according to the conditions of method (a) is implemented.

In addition, in process (c) according to the invention as starting materials Compounds using are generally defined by formula (VII). In this Formula Het, Y and p are preferred, particularly preferred or very particularly preferred for those meanings that are already in connection with the Description of the compounds of formula (I) according to the invention for these radicals have been mentioned as preferred, particularly preferred or very particularly preferred. m preferably represents 0 or 1. Q preferably represents those meanings which already in connection with the description of the 4-aminopyridines of the formula (IV) were mentioned as preferred for these residues.

The compounds of formula (VII) are obtained by using bromides of Formula (V) with boron derivatives of the formula (IX) according to the conditions of Process (c) implemented.

The acid binders used in carrying out the process (a, variant 1) all common inorganic and organic bases in question. Preferably Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates can be used, acetates, carbonates or bicarbonates, such as sodium hydride, sodium amide, Sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, Potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, Potassium carbonate, potassium hydrogen carbonate, also 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 diazabicycloundecene (DBU).

The diluents used in carrying out the process (a, Variant 1) all inert, organic solvents. Preferably usable are aliphatic, alicyclic or aromatic hydrocarbons, such as Petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, Dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ether like Diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, Tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, like Acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N- Dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane.

The reaction temperatures can be carried out when carrying out process (a, Variant 1) can be varied within a larger range. Generally works one at temperatures between 0 ° C and + 120 ° C, preferably between 20 ° C and 80 ° C.

The procedure (a, variant 1) is generally carried out with equimolar amounts or a small excess of halogenating agent and acid binders. The processing takes place according to usual methods. in the generally one proceeds in such a way that the reaction mixture after the The reaction is concentrated, the remaining residue with water and one with water little miscible organic solvent added, the organic phase separates, washes, dries and concentrates. The remaining product can be made according to usual Methods are freed of any contaminants.

When carrying out the process (a, variant 2), all come as catalysts usual reaction accelerators in question, which are used to activate the carboxyl group of the phenylacetic acid derivative of the formula (III) are suitable. Preferably Carbonyldiimidazole and di-cyclohexyl-carbodiimide can be used. Furthermore can the implementation is carried out in the presence of water-binding agents become.

The diluents used in carrying out the process (a, Variant 2) all inert organic solvents customary for such reactions in Consideration. Aliphatic, alicyclic or aromatic are preferably usable 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.

The reaction temperatures can be carried out when carrying out process (a, Variant 2) can be varied within a certain range. In general one works at temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 80 ° C.

The procedure (a, variant 2) is generally carried out with equimolar amounts. However, it is also possible to use one or the other To use component in excess. The processing takes place according to usual Methods. In general, one proceeds in such a way that one of the failed Aspirated solid, the filtrate is concentrated under reduced pressure and the remaining residue chromatographed.

Suitable diluents for carrying out the inventive Processes (b) and (c) are all inert under the given reaction conditions organic solvents. You can optionally mix with Water can be used. Hydrocarbons such as are preferably used Toluene, xylene, tetralin, hexane, cyclohexane, halogenated hydrocarbons such as Methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, ethers such as diethyl ether, Diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxane, nitriles such as acetonitrile or butyronitrile, amides such as dimethylformamide and also sulfolane.

The base used in carrying out processes (b) and (c) all common acid acceptors in question. Tertiary are preferably used Amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicyclo- undecene (DBU), diazabicyclonones (DBN), N, N-dimethylaniline, further Alkaline earth metal oxides such as magnesium or calcium oxide, also alkali and Alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, Alkali hydroxides such as sodium or potassium hydroxide, furthermore alcoholates such as Sodium ethanolate or potassium tert-butoxide.

The catalysts used in carrying out the process of the invention (b) and (c) Palladium or its compounds or complexes, preferably Tetrakis (triphenylphosphine) palladium or 1,1 '- [bis (diphenylphosphino) ferrocene] dichloropalladium.

The reaction temperatures can be carried out when the inventive Processes (b) and (c) can be varied over a wide range. In general one works at temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 80 ° C or at the boiling point of the solvent used. When carrying out processes (b) and (c) according to the invention, the process is carried out in generally in equimolar amounts, optionally from 0.01 to 0.1 mol Catalyst and 1 to 5 mol of base can be used.

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

With good plant tolerance and favorable toxicity to warm-blooded animals, the active substances are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They 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 z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus.
From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spp ..
From the order of the Symphyla z. B. Scutigerella immaculata.
From the order of the Thysanura z. B. Lepisma saccharina.
From the order of the Collembola z. B. Onychiurus armatus.
From the order of the Orthoptera z. B. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
From the order of the Blattaria z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Reticulitermes spp ..
From the order of the Phthiraptera z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp ..
From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
From the order of the Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus sppe, Phosiphodumumpp., Macrosiphumum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisppina, Fpp , Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Hofeamannellellaella, Hofeamannellaellaella, Tinea pellionella Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.
From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephppis, Orphusus spp. , Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Giptusibbium psol. Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.
From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomox ., Oestrus spp., Hypoderma 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 z. B. Xenopsylla cheopis, Ceratophyllus spp ..
From the class of the Arachnida z. B. Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommodes spp., I ., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp ..
Plant parasitic nematodes include e.g. B. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Burs

The substances according to the invention can be used with particularly good success Control of harmful insects, such as. B. against the larvae of 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), the cotton aphid (Aphis gossypii) and the Peach aphid (Mycus persicae) or to combat plant-damaging Use mites as against bean spider mite (Tetranychus urticae).

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

Fungicides can be used to protect plants against Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Use Deuteromycetes.

Bactericides can be used in plant protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae deploy.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
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 cubensis;
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 graminis;
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. graminea (conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus 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 sclerotiorum;
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 infestation by unwanted microorganisms.

Among plant-strengthening (resistance-inducing) substances are in the present To understand the context of such substances that are able to Defense system of plants to stimulate the treated plants subsequent inoculation with undesirable microorganisms Develop resistance to these 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 plant after a certain period of time Protect treatment against infestation by the named pathogens. The 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 ingredients.

The good plant tolerance of the active ingredients in the fight against Concentrations necessary for plant diseases allow treatment of above-ground parts of plants, of seedlings, and of the soil.

The active compounds according to the invention can be particularly successful Combat cereal diseases such as mildew and rust use as well 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 on.

The active compounds according to the invention can, if appropriate, in certain Concentrations and application rates also as herbicides, to influence the Plant growth, as well as for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis use other active ingredients.

According to the invention, all plants and parts of plants can be treated. Under Plants are understood here as all plants and plant populations desired and undesirable wild plants or crops (including naturally occurring crops). Cultivated plants can be plants that by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods can be obtained, including and including the transgenic plants plant varieties that can or cannot be protected by plant breeders' rights. Plant parts should include all above-ground and underground parts and organs of plants, such as sprout, leaf, flower and root are understood, whereby exemplary leaves, needles, stems, stems, flowers, fruiting bodies, fruits and Seeds as well as roots, tubers and rhizomes are listed. To the Plant parts also include crops, vegetative and generative propagation material, for example cuttings, tubers, rhizomes, cuttings and seeds.

The treatment of the plants and plant parts according to the invention with the Active substances take place directly or by influencing their environment, habitat or Storage room according to the usual treatment methods, e.g. B. by diving, spraying, Evaporation, atomization, scattering, spreading and in the case of propagation material, especially in the case of seeds, further by single or multi-layer coating.

In material protection, the substances according to the invention can be used to protect technical materials against infestation and destruction by unwanted Use microorganisms.

In the present context, technical materials include non-living ones Understand materials that have been prepared for use in engineering are. For example, technical materials can be produced by the invention Active substances are to be protected against microbial change or destruction, Adhesives, glues, paper and cardboard, textiles, leather, wood, paints and Plastic items, coolants and other materials may be those of Microorganisms can be attacked or decomposed. As part of the to be protected Materials are also parts of production plants, for example Cooling water circuits, called, impaired by the multiplication of microorganisms can be. In the context of the present invention are considered technical Materials preferably adhesives, glues, papers and boxes, leather, wood, Paints, cooling lubricants and heat transfer fluids called particularly preferably wood.

As microorganisms that break down or change the technical Bacteria, fungi, yeasts, algae can cause materials and called mucus organisms. The agents according to the invention preferably act Active ingredients against fungi, in particular mold, wood-staining and wood-destroying fungi (Basidiomycetes) and against mucus organisms and algae.

Microorganisms of the following genera may be mentioned, for example:
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,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.

The active ingredients can depend on their respective physical and / or chemical properties converted into the usual formulations such as solutions, emulsions, suspensions, powders, foams, pastes, Granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, under pressure standing liquefied gases and / or solid carriers, optionally under Use of surface-active agents, i.e. emulsifiers and / or Dispersing agents and / or foaming agents. In case of using water as Extenders can e.g. B. also organic solvents as auxiliary solvents be used. 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, e.g. B. 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. With Liquefied gaseous extenders or carriers are such liquids meant which are gaseous at normal temperature and pressure, z. B. aerosol propellants, such as halogenated hydrocarbons and butane, propane, Nitrogen and carbon dioxide. Possible solid carriers are: B. natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse Silica, alumina and silicates. Coming as solid carriers for granules in question: e.g. B. broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules made of organic material such as sawdust, Coconut shells, corn cobs and tobacco stems. As an emulsifier and / or Foaming agents are possible: z. B. nonionic and anionic emulsifiers, such as Polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersants are: B. lignin sulfite and Methylcellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural Phospholipids such as cephalins and lecithins, and synthetic phospholipids. Further Additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. 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 can be used, e.g. B. the spectrum of activity broaden or prevent the development of resistance. In many cases you get it synergistic effects, d. H. the effectiveness of the mixture is greater than that Effectiveness of the individual components.

The following compounds, for example, are possible as mixing 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), chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymroconililanil
Debacarb, dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxin, dithorphononodine,
Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,
Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazol, flurprimidololol, flurprimidolanilus, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidolutolol Aluminum, fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,
Guazatin, hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Iprovalicarb, Irumamycin, Isoprothiolan, Isovaledione,
Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
Paclobutrazol, pefurazoate, penconazole, pencycuron, phosdiphen, picoxystrobin, PIMARICIN, piperalin, polyoxin, Polyoxorim, probenazole, prochloraz, procymidone, propamocarb, Propanosine sodium, propiconazole, propineb, pyraclostrobin, Pyrazohos, pyrifenox, pyrimethanil, pyroquilon, Pyroxyfur,
Quinconazole, quintozen (PCNB), quinoxyfen,
Sulfur and sulfur preparations, spiroxamines,
Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, 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, viniconazole,
Zarilamid, Zineb, Ziram as well
Dagger G, OK-8705, OK-8801,
α- (1,1-dimethylethyl) -β- (2-phenoxyethyl) -1H-1,2,4-triazole-1-ethanol,
a- (2,4-dichlorophenyl) -β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,
α- (5-methyl-1,3-dioxan-5-yl) -β - [[4- (trifluoromethyl) phenyl] methylene] -1H-1,2,4-triazol-1-ethanol,
(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-1,2,4-triazol-1-yl) -3-octanone,
(E) -α- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,
1- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) oxime,
1- (2-methyl-1-naphthalenyl) -1H-pyrrole-2,5-dione,
1- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione,
1 - [(diiodomethyl) sulphonyl] -4-methylbenzene,
1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-imidazole,
1 - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -1H-1,2,4-triazole,
1- [1- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1H-imidazole,
1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,
2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide,
2,6-dichloro-5- (methylthio) -4-pyrimidinyl thiocyanate,
2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide,
2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,
2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,
2 - [(1-methylethyl) sulphonyl] -5- (trichloromethyl) -1,3,4-thiadiazole,
2 - [[6-Deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -α-D-glucopyranosyl] amino] -4- methoxy-1H-pyrrolo [2,3-d] pyrimidine-5-carbonitrile,
2-aminobutane,
2-bromo-2- (bromomethyl) -pentandinitril,
2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridine carboxamide,
2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) -acetamide,
2-phenylphenol (OPP),
3,4-dichloro-1- [4- (difluoromethoxy) phenyl] -1H-pyrrole-2,5-dione,
3,5-dichloro-N- [cyano ((1-methyl-2-propynyl) -oxy] -methyl] -benzamide,
3- (1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] -pyridine,
4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazo-1-sulfonamide,
4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,
8-hydroxyquinoline sulfate,
9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide,
bis (1-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) oxy] -2,5-thiophene dicarboxylate,
cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol,
cis-4- [3- [4- (1,1-dimethylpropyl) -phenyl-2-methylpropyl] -2,6-dimethyl-morpholine,
Ethyl - [(4-chlorophenyl) azo] cyanoacetate,
potassium bicarbonate,
Methantetrathiol sodium salt,
Methyl-1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate,
Methyl-N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,
Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,
N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,
N- (4-Cyclohexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (4-hexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) -acetamide,
N- (6-methoxy) -3-pyridinyl) -cyclopropanecarboxamide,
N- [2,2,2-trichloro-1 - [(chloroacetyl) -amino] -ethyl] -benzamide,
N- [3-chloro-4,5-bis- (2-propynyloxy) -phenyl] -N'-methoxy-methanimidamid,
N-formyl-N-hydroxy-DL-alanine-sodium salt,
O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat,
O-methyl-S-phenyl-phenylpropylphosphoramidothioate,
S-Methyl-1,2,3-benzothiadiazole-7-carbothioate,
spiro [2H] -1-benzopyran-2,1 '(3'H) -isobenzofuran] -3'-one,
4- [3,4-dimethoxyphenyl) -3- (4-fluorophenyl) acryloyl] morpholine bactericidal bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam and others, copper sulfate copper preparations. Insecticides / Acaricides / Nematicides Abamectin, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos M, Azinphos M,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Bioethanomifhrin, Bethenomifhrin, Bethenomifhrin, Bethanomifhrin , Butocarboxime, butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Chlovaporthrin, Chromafenozide, Cis-Resmethrin, Clofocytoprene, Cofocenthrin, Cofocenthrin, Cofocenthrin, Cofocenthrin , Cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Dicofol, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn,
Eflusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos,
Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazuron, Flubrocythrinate, Flucycloxuron, Flytoxhrhrininate, Fumetoxinhrinate, Foncythrinate, Foncythrinate, Foncythrinate, Foncythrininate, Fonetoxin , Furathiocarb,
granulosis
Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
Imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin,
Nuclear polyhedron viruses, lambda cyhalothrin, lufenuron
Malathion, Mecarbam, Metaldehyde, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methoprene, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Milbemycin, Monocrotophos,
Naled, Nitenpyram, Nithiazine, Novaluron
Omethoate, oxamyl, oxydemethone M
Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propargite, Propoxur, Prothiofos, Prothrohrinos, Pothrohrinos, Pothrohrinos, Pothrohrinos , Pyridaben, pyridathione, pyrimidifen, pyriproxyfen,
quinalphos,
ribavirin
Salithion, Sebufos, Silafluofen, Spinosad, Spirodiclofen, Sulfotep, Sulprofos,
Tau-fluvalinate, tebufenozide, tebufenpyrad, Tebupirimiphos, teflubenzuron, tefluthrin, temephos, Temivinphos, terbufos, tetrachlorvinphos, tetradifon Thetacypermethrin, thiacloprid, thiamethoxam, Thiapronil, Thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, Tralocythrin, tralomethrin, triarathene, Triazamate , Triazophos, triazuron, trichlophenidines, trichlorfon, triflumuron, trimethacarb,
Vamidothion, Vaniliprole, Verticillium lecanii
YI 5302
Zeta-cypermethrin, zolaprofos
(1R-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate
(3-phenoxyphenyl) methyl-2,2,3,3-tetramethylcyclopropanecarboxylat
1 - [(2-Chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2 (1H) - imine
2- (2-chloro-6-fluorophenyl) -4- [4- (1,1-dimethylethyl) phenyl] -4,5-dihydro-oxazol
2- (Acetlyoxy) -3-dodecyl-1,4-naphthalenedione
2-chloro-N - [[[4- (1-phenylethoxy) phenyl] amino] carbonyl] -benzamide
2-chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) phenyl] amino] carbonyl] -benzamide
3-methylphenyl propylcarbamate
4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene
4-Chloro-2- (1,1-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] - 3 (2H) pyridazinone
4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone
4-chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichlorophenyl) -3 (2H) -pyridazinone
Bacillus thuringiensis strain EG-2348
Benzoic acid [2-benzoyl-1- (1,1-dimethylethyl) hydrazide
Butanoic acid 2,2-dimethyl-3- (2,4-dichlorophenyl) -2-oxo-1-oxaspiro [4.5] dec-3-en-4-yl ester
[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] -cyanamide
Dihydro-2- (nitromethylene) -2H-1,3-thiazine-3 (4H) -carboxaldehyde
Ethyl [2 - [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] carbamate
N- (3,4,4-trifluoro-1-oxo-3-butenyl) -glycine
N- (4-chlorophenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide
N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine
N-methyl-N '- (1-methyl-2-propenyl) -1,2-hydrazindicarbothioamid
N-methyl-N'-2-propenyl-1,2-hydrazindicarbothioamid
O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat
N-cyanomethyl-4-trifluoromethyl-nicotinamide
3,5-dichloro-1- (3,3-dichloro-2-propenyloxy) -4- [3- (5-trifluoromethylpyridin-2-yloxy) propoxy] benzene

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

In addition, the compounds of the formula (I) according to the invention also very good antifungal effects. They have a very broad one antifungal activity spectrum, especially against dermatophytes and fungi, Mold and diphasic fungi (e.g. against Candida species such as Candida albicans, Candida glabrata) and Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species like Trichophyton mentagrophytes, microsporon species such as microsporon canis and audouinii. The The list of these mushrooms in no way places a restriction on what can be detected mycotic spectrum, but is only explanatory.

The active substances can be used as such, in the form of their formulations or in the form thereof prepared application forms, such as ready-to-use solutions, suspensions, Spray powder, pastes, soluble powders, dusts and granules can be used. The Application is done in the usual way, e.g. B. by pouring, spraying, Spraying, scattering, dusting, foaming, brushing etc. It is also possible apply the active ingredients according to the ultra-low-volume process or the Active ingredient preparation or to inject the active ingredient yourself into the soil. It can also the seeds of the plants are treated.

When using the active compounds according to the invention as fungicides, the Application rates can be varied within a wide range depending on the type of application. When treating parts of plants, the amounts of active ingredient are in the 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 in the 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 floor the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

When used as insecticides, the active compounds according to the invention can also be used in their commercial formulations and in those formulations prepared application forms in a mixture with synergists. synergists are compounds that increase the effectiveness of the active ingredients without the added synergist itself must be active.

The active substance content of those prepared from the commercially available formulations Application forms can vary widely. The drug concentration of the Use forms can be from 0.0000001 to 95% by weight of active compound, preferably are between 0.0001 and 1% by weight.

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

When used against hygiene and storage pests, the Active ingredient through an excellent residual effect on wood and clay as well as through good stability to alkali on limed substrates.

As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, go wild occurring or by conventional organic breeding methods, such as crossing or Protoplast fusion obtained plant species and plant varieties and their parts treated. In a further preferred embodiment, transgenes are Plants and plant varieties, if necessary by genetic engineering methods in combination with conventional methods (Genetic Modified Organisms) and their parts treated. The term "parts" or "parts of." Plants "or" parts of plants "was explained above.

Plants of the commercially available in each case are particularly preferred according to the invention or plant varieties in use. Among plant varieties is understood to mean plants with new properties ("traits") that are characterized by both conventional breeding, by mutagenesis or by recombinant DNA techniques have been bred. These can be varieties, breeds, bio and genotypes.

Depending on the plant species or plant varieties, their location and Growth conditions (soils, climate, growing season, nutrition) can be determined by the Treatment according to the invention also has superadditive ("synergistic") effects occur. For example, reduced application rates and / or extensions of the Spectrum of activity and / or an enhancement of the effect of the invention usable substances and agents, better plant growth, increased tolerance against high or low temperatures, increased tolerance to drought or against water or soil salt content, increased flowering performance, easier harvesting, Acceleration of ripeness, higher crop yields, higher quality and / or higher Nutritional value of the harvested products, higher shelf life and / or workability of the harvested products possible, which have the expected effects go out.

Among the preferred transgenic (genetic engineering received) plants or plant varieties include all plants by the genetic engineering modification received genetic material that this Gives plants special beneficial valuable properties ("traits"). Examples for such properties are better plant growth, increased tolerance against high or low temperatures, increased tolerance to drought or against water or soil salt content, increased flowering performance, easier harvesting, Acceleration of ripeness, 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 against plants and animals microbial pests, such as insects, mites, phytopathogenic fungi, Bacteria and / or viruses and an increased tolerance of the plants to certain herbicidal active ingredients. The important ones are examples of transgenic plants Crops, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, Rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and Grapes) mentioned, especially corn, soybeans, potatoes, cotton and rapeseed be highlighted. As properties ("traits") become special highlighted the increased defense of plants against insects by in the Plant-derived toxins, especially those caused by the genetic material from Bacillus thuringiensis (e.g. by the genes CryIA (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF as well as their Combinations) are generated in the plants (hereinafter "Bt plants"). As Properties ("traits") are also particularly emphasized the increased defense of plants against fungi, bacteria and viruses by systemic acquirers Resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and appropriately expressed proteins and toxins. As traits further emphasized the increased tolerance of plants certain herbicidal active ingredients, for example imidazolinones, Sulfonylureas, glyphosate or phosphinotricin (e.g. "PAT" gene). The each the genes imparting the desired traits can also be found in Combinations with each other occur in the transgenic plants. As examples for "Bt plants" are maize varieties, cotton varieties, soy varieties and potato varieties under the trade names YIELD GARD® (e.g. maize, Cotton, soy), KnockOut® (e.g. maize), StarLink® (e.g. maize), Bollgard® (Cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are maize, cotton and Soybeans known as Roundup Ready® (Tolerance to glyphosates e.g. corn, cotton, soy), Liberty Link® (tolerance against phosphinotricin, e.g. Rape), IMI® (tolerance to imidazolinones) and STS® (Tolerance to sulfonylureas e.g. maize). As a herbicide resistant (conventionally grown to herbicide tolerance) plants are also the varieties sold under the name Clearfield® (e.g. maize). Of course, these statements also apply to future developed or future plant varieties with these or in the future developed genetic traits.

The plants listed can be particularly advantageous according to the invention with the Compounds of the general formula (I) or those according to the invention Active ingredient mixtures are treated. The above for the active ingredients or mixtures Preferred ranges given also apply to the treatment of these plants. Plant treatment with those in the present text should be particularly emphasized Specially listed compounds or mixtures.

The active compounds according to the invention act not only against pests from plants, hygiene and stored products, but also in the veterinary sector against animal parasites (ectoparasites) such as tick 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 z. B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp ..
From the order of the Mallophagida and the subordinates Amblycerina and Ischnocerina z. B. 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 and Brachycerina z. B. 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 z. B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp ..
From the order of the Heteropterida z. B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp ..
From the order of the Blattarida z. B. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp ..
From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata z. B. 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) z. B. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp. Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..

The active compounds of the formula (I) according to the invention are also suitable for combating of arthropods, the farm animals, such as. B. cattle, sheep, goats, Horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, Bees, other pets such as B. dogs, cats, house birds, aquarium fish as well as so-called experimental animals, such as. B. hamsters, guinea pigs, rats and Infest mice. By fighting these arthropods, deaths and Reductions in performance (for meat, milk, wool, skins, eggs, honey, etc.) can be reduced, so that by using the active compounds according to the invention more economical and easier animal husbandry is possible.

The active compounds according to the invention are used in the veterinary sector in in a known manner by enteral administration in the form of, for example, tablets, Capsules, watering, drenching, granules, pastes, boluses, the feed-through process, suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, through nasal Application, by dermal application in the form of, for example, diving or Bathing (dipping), spraying (spray), pouring (pour-on and spot-on), des Washing, powdering and with the help of shaped articles containing active ingredients, such as Collars, ear tags, tail tags, limb straps, holsters, Marking devices etc.

When used for cattle, poultry, pets etc., you can use the active ingredients in Formula (I) as formulations (for example powders, emulsions, flowable Agents), which contain the active ingredients in an amount of 1 to 80 wt .-%, directly or after 100 to 10,000-fold dilution or use it as a chemical bath use.

It was also found that the compounds of the invention have a high Show insecticidal activity against insects that destroy technical 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, Lyctus pubis linearis, speculum Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.
Skin wing 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 cardboard, leather, wood, wood processing products and paints.

The one to be protected against insect attack is very particularly preferably Material around wood and wood processing products.

Wood and wood processing products that 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 wooden products that are generally used in house construction or joinery.

The active ingredients can be used as such, in the form of concentrates or in general usual formulations such as powders, granules, solutions, suspensions, Emulsions or pastes can be applied.

The formulations mentioned can be prepared in a manner known per se be, e.g. B. by mixing the active ingredients with at least one solution or Diluents, emulsifiers, dispersants and / or binders or fixatives, Water repellants, possibly desiccants and UV stabilizers and optionally dyes and pigments and other processing aids.

The insecticidal agents or used to protect wood and wood-based materials Concentrates contain the active ingredient according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.

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

An organic chemical is used as the solvent and / or diluent Solvent or solvent mixture and / or an oily or oily heavy 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, used. As such volatile, Water-insoluble, oily and oily solvents become corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene used.

Mineral oils with a boiling range of 170 to 220 ° C are advantageous, White spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range from 250 to 350 ° C, petroleum or aromatics with a boiling range from 160 to 280 ° C, Turpentine oil and the like.

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

The organic non-volatile oily or oily solvents with a Evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be caused in part by easily or moderately volatile organic chemical solvents are replaced, with the proviso that the Solvent mixture also has an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide fungicide Mixture is soluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, part of the organic chemical Solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture replaced. Preferably come aliphatic containing hydroxyl and / or ester and / or ether groups organic chemical solvents such as glycol ether, ester or the like. to use.

As organic-chemical binders in the context of the present Invention known per se and / or used in the water-dilutable organochemical solvents soluble or dispersible or emulsifiable Synthetic resins and / or binding drying oils, in particular binders from or containing an acrylic resin, a vinyl resin, e.g. B. 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 in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10 wt .-%, are used. In addition, in itself known dyes, pigments, water repellants, odor correctors and Inhibitors or anticorrosive agents and the like are used.

According to the invention, preference is given to at least one organic chemical binder an alkyd resin or modified alkyd resin and / or a drying vegetable Contain oil in the medium or in the concentrate. Are preferred according to the invention Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight.

The binder mentioned can be wholly or partly by a Fixing agent (mixture) or a plasticizer (mixture) can be replaced. These additions should volatilize the active ingredients and crystallize or precipitate prevent. 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, glycerol ether or higher molecular weight Glycol ether, glycerol ester and p-toluenesulfonic acid ester.

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

Water is also particularly suitable as a solvent or diluent, optionally 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, z. B. vacuum, double vacuum or printing process.

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

The additional mixing partners are preferably those in WO 94/29 268 Insecticides and fungicides mentioned in question. The ones mentioned in this document Connections are an integral part of this application.

Insecticides, such as chlorpyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiaphenoxonifonif, trifluoropuron, trifluoropurin
as well as fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorofluoride, tolylfluanid, 3-iodo-2-propynylbutylcarbamate, N-octyl-isothiazolin-3-one and 4,5- - octylisothiazolin-3-one.

At the same time, the compounds according to the invention can protect against fouling objects, in particular hulls, sieves, nets, structures, Quayside and signal systems, which are connected with sea or brackish water come, be used.

Overgrowth by sessile oligochaetes, such as lime tube worms and by mussels and species of the Ledamorpha (barnacles) group, such as various Lepas and Scalpellum species, or by species from the group Balanomorpha (barnacles), such as Balanus or pollicipes species, increases the frictional resistance of ships and subsequently leads through increased energy consumption and moreover through frequent Dry dock stays for a significant increase in operating costs.

In addition to the growth by algae, for example Ectocarpus sp. and Ceramium sp., comes in particular the vegetation by sessile Entomostraken groups, which under the name Cirripedia (barnacles) special meaning too.

It has now surprisingly been found that the inventive Compounds alone or in combination with other active ingredients, an excellent Have antifouling effect.

By using compounds according to the invention alone or in combination with other active ingredients, can rely on the use of heavy metals such. B. in bis- (trialkyltin) sulfides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper (I) oxide, Triethyltin chloride, tri-n-butyl (2-phenyl-4-chlorophenoxy) tin, tributyltin oxide, Molybdenum disulfide, antimony oxide, polymeric butyl titanate, Phenyl (bispyridine) bismuth chloride, tri-n-butyltin fluoride, manganese ethylene bisthiocarbamate, Zinc dimethyldithiocarbamate, zinc ethylene bisthiocarbamate, zinc and copper salts of 2-pyridinthiol-1-oxide, bisdimethyldithiocarbamoylzinkethylenbisthiocarbamate, zinc oxide, Copper (I) ethylene bisdithiocarbamate, copper thiocyanate, copper naphthenate and Tributyltin halides are omitted or the concentration of these compounds be significantly reduced.

The ready-to-use antifouling paints can also be used if necessary Active ingredients, preferably algicides, fungicides, herbicides, molluscicides or others Contain antifouling ingredients.

Suitable combination partners for the antifouling agents according to the invention are preferably:
Algicides like
2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophene, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;
Fungicides like
Benzo [b] thiophenecarboxylic acid cyclohexylamide-S, S-dioxide, dichlofluanid, fluorfolpet, 3-iodo-2-propynyl-butylcarbamate, tolylfluanid and azoles such as azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and ticon;
Molluscicides like
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-dimethylthiocarbamoylthio) -5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinthiol-1 -oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 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 ingredient according to the invention compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular from 0.01 to 20% by weight.

The antifouling agents according to the invention furthermore contain the usual ones Components such as B. in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

Antifouling paints contain algicidal, fungicidal, molluscicides and insecticidal active substances according to the invention, in particular binders.

Examples of recognized binders are polyvinyl chloride in one Solvent system, chlorinated rubber in one solvent system, acrylic resins in one Solvent system especially in an aqueous system, Vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / 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 Chlorinated rubber, chlorinated polypropylene and vinyl resins.

Paints may also contain inorganic pigments, organic Pigments or dyes, which are preferably insoluble in sea water. Further Paints can contain materials, such as rosin, to be controlled To enable release of the active ingredients. The paintings can also Plasticizers, modifiers influencing the rheological properties as well as other conventional ingredients. Even in self-polishing Antifouling systems can use the compounds according to the invention or the above mentioned mixtures are incorporated.

The active ingredients are also suitable for controlling animal pests, in particular insects, arachnids and mites, which live in closed spaces, such as, for example, apartments, factory halls, offices, vehicle cabins and the like. occur. To combat 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 z. B. Buthus occitanus.
From the order of Acarina z. B. 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 z. B. Aviculariidae, Araneidae.
From the order of the Opiliones z. B. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
From the order of the Isopoda z. B. Oniscus asellus, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus, Polydesmus spp ..
From the order of the Chilopoda z. B. Geophilus spp ..
From the order of the Zygentoma z. B. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
From the order of the Blattaria z. B. 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 z. B. Acheta domesticus.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Kalotermes spp., Reticulitermes spp.
From the order of Psocoptera z. B. Lepinatus spp., Liposcelis spp.
From the order of the Coleptera z. B. 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 z. B. Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis. , Stomoxys calcitrans, Tipula paludosa.
From the order of the Lepidoptera z. B. Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
From the order of the Siphonaptera z. B. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
From the order of the Hymenoptera z. B. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
From the order of the Anoplura z. B. Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis.
From the order of the Heteroptera z. B. Cimex hemipterus, Cimex 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 ingredients from other known Classes of insecticides.

The application takes place in aerosols, unpressurized sprays, e.g. B. Pump and Atomizer sprays, automatic fog machines, foggers, foams, gels, Vaporizer products with vaporizer platelets made of cellulose or plastic, liquid vaporizers, Gel and membrane evaporators, propeller-driven evaporators, energy-free or passive evaporation systems, moth papers, moth bags and Moth angels, as granules or dusts, in lures or bait stations.

The manufacture and use of the substances according to the invention are based on following examples.

Preparation Examples example 1

Procedure a / variant 1

To a solution of 3.2 g (0.0123 mol) 4- (2-tert-Butyl-tetrazol-5-yl) -phenyl-acetic acid in 80 ml of methylene chloride is added to 1.6 g (0.0137 mol) of thionyl chloride. Then the mixture is 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 Methylene chloride. With cooling, this solution is added at 0 ° C. to a solution of 1.9 g (0.0123 mol) 2-ethyl-3-chloro-4-aminopyridine and 1.4 g (0.014 mol) triethylamine in 50 ml methylene chloride. The reaction mixture is at for 16 hours Stirred at room temperature, then evaporated in vacuo and the residue with Ethyl acetate and water shaken. The organic phase is over Dried sodium sulfate and evaporated in vacuo. The residue is cleaned through Silica gel chromatography (methylene chloride / methanol 7: 1).

0.9 (18% of theory) of 4- (2-tert-butyl-tetrazol-5-yl) -phenylacetic acid-N- (2-ethyl-3-chloro-pyrid-4-yl) is thus obtained ) -amide in the form of a colorless solid with the logP (pH2) = 2.34. Manufacture of the starting product

A mixture of 6.9 g (0.034 mol) of 4- (tetrazol-5-yl) phenylacetic acid, 75 ml Trifluoroacetic acid, 14.8 g (0.2 mol) tert-butanol and 1.85 ml conc. Sulfuric acid stirred for 16 hours at room temperature. Then you steam it Reaction mixture in a vacuum and shake the residue with ethyl acetate and Water. The organic phase is dried over sodium sulfate and in vacuo evaporated. 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 (pH2) = 2.18. Production of the preliminary product

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 cooked under reflux for 16 hours. Then you cool down to room temperature, decant the organic phase and add 100 ml of 5% to the oily residue Sodium hydroxide solution. The solution is then filtered through Celite and the filtrate is acidified dilute hydrochloric acid. The precipitated product is suctioned off and with water rewashed.

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

Procedure a / variant 2

To a solution of 1.5 g (6.6 mmol) of 4- (4-cyano-pyrazol-1-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-chloro-4-aminopyridine was added in portions and the mixture was added for 18 hours Reflux cooked. Then the solvent is evaporated off in vacuo and shake the residue with ethyl acetate and water. The organic phase is dried over sodium sulfate and evaporated in vacuo. The backlog is purified by silica gel chromatography.

This gives 0.1 g (4% of theory) of 4- (4-cyano-pyrazol-1-yl) phenylacetic acid N- (2-ethyl-3-chloropyrid-4-yl) - amide in the form of beige crystals with the logP (pH2) = 1.60. Manufacture of the starting product

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) 2-hydroxymethylene-3,3-dimethoxypropionitrile sodium salt (preparation see EP 279 556) and added for 16 hours Room temperature stirred. Then the mixture is refluxed for 2 hours cooked and then evaporated in vacuo. The residue is triturated with water and then sucks off the failed product.

13.1 g (87% of theory) of 4- (4-cyano-pyrazol-1-yl) phenylacetic acid are thus obtained in the form of a beige powder with the logP (pH2) = 1.46. Example 3

Procedure b

To a solution of 1 g (2.5 mmol) of 4- (4,4,5,5, tetramethyl-1,3,2-dioxaborolan-2- yl) phenylacetic acid-N- (2-ethyl-3-chloropyrid-4-yl) -amide and 0.7 g (3 mmol) 2-methoxy-5-bromopyridine in 60 ml of 1,2-dimethoxyethane is added under an argon atmosphere 0.1 g 1,1 '- [bis (diphenylphosphino) ferrocene] dichloropalladium dichloromethane complex and 5 ml 2M sodium carbonate solution. The mixture is left for 16 hours 80 ° C stirred. Then the reaction mixture is filtered through Celite and the filtrate evaporated in vacuo. The residue is cleaned through Silica gel chromatography (methylene chloride / ethyl acetate 1: 1).

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. Manufacture of the starting product

To a solution of 7 g (0.02 mol) 4-bromophenylacetic acid-N- (2-ethyl-3-chloropyrid-4-yl) -amide in 150 ml of dioxane is added at room temperature to 5.9 g (0.06 mol) Potassium acetate, 5.5 g (0.022 mol) bis (pinacolato) diborane, 0.4 g 1,1 '- [bis (diphenylphosphino) ferrocene] dichloropalladium dichloromethane complex and 0.3 g of 1,1'-bis (diphenylphosphino) ferrocene and the mixture is stirred at 80 ° C. for 21 hours. Then the reaction mixture is poured onto water and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and in vacuo evaporated. The residue is triturated with disiopropyl ether and sucked failed product.

4.8 g (60% of theory) of 4- (4,4,5,5-tetramethyl-1,3,2-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 preliminary product

To a solution of 10.8 g (0.05 mol) of 4-bromophenylacetic acid in 100 ml of dioxane 9.7 g (0.06 mol) are added as a batch at room temperature N ', N'-carbonyl-diimidazole and the mixture is stirred for 1 hour at room temperature. Then be 7.4 g ((0.045 mol)) of 2-ethyl-3-chloro-4-aminopyridine were added in portions and the Mixture refluxed for 1 hour. Then the solvent is evaporated in a vacuum and shake the residue with ethyl acetate and water. The organic phase is dried over sodium sulfate and in vacuo evaporated. The residue is recrystallized from acetonitrile.

5.9 g (35% of theory) are thus obtained 4-Bromophenylacetic acid-N- (2-ethyl-3-chloropyrid-4-yl) -amide 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 determination of those in the tables and manufacturing examples above specified logP values are carried out in accordance with EEC Directive 79/831 Annex V.48 HPLC (High Performance Liquid Chromatography) on a phase reversal column (C18). 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 of 10% acetonitrile up to 90% acetonitrile.

The calibration takes place with unbranched alkan-4-ones (with 3 to 16 Carbon atoms) whose logP values are known (determination of the logP values using the Retention time by linear interpolation between two successive ones Alkanones).

applications Example A Aphis gossypii test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water containing emulsifier to the desired level Concentration.

Cotton leaves (Gossypium hirsutum) that are heavily affected by the cotton aphid (Aphis gossypii) are infested, are immersed in the preparation of the active ingredient desired concentration treated.

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

This test shows at an exemplary drug concentration of 500 ppm z. B. the compound 1 of the production examples a kill of 100% and the Compound 20 of the production examples had a kill rate of 95%, in each case after 6 Days.

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 prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate to the desired level with water containing emulsifier Concentration.

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

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

This test shows at an exemplary drug concentration of 500 ppm z. B. the compound 1 of the preparation examples after 10 days a kill of 100%.

Example C Heliothis virescens test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate to the desired level with water containing emulsifier Concentration.

Soybean shoots (Glycine max) are dipped into the active ingredient preparation desired concentration treated and populated with Heliothis virescens caterpillars, as long as the leaves are still damp.

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

This test shows at an exemplary drug concentration of 500 ppm z. B. the compound 7 of the manufacturing examples after 7 days a kill of 100%.

Example D Meloidogyne Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

Vessels are covered with sand, active ingredient solution, Meloidogyne incognita egg larvae Suspension and lettuce seeds filled. The lettuce seeds germinate and the little plants develop. The galls develop at the roots.

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

This test shows at an exemplary active ingredient concentration of 500 ppm z. B. 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 manufacturing examples after 100 days a 100% kill.

Example E Myzus test (systemic effect)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate to the desired level with water containing emulsifier Concentration.

With 10 ml of active ingredient preparation of the desired concentration Savoy cabbage plants (Brassica oleracea), heavily of the green peach aphid (Myzus persicae) are cast on, so that the active ingredient preparation in the Soil penetrates without wetting the sprout. The active ingredient comes from the roots recorded and forwarded to the sprout.

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

This test shows at an exemplary active ingredient concentration of 500 ppm z. B. the compounds 1, 11, 27 and 36 of the preparation examples a killing of 95%, the compounds 24 and 32 of the preparation examples a kill of 98 % and compound 34 of the preparation examples have a kill rate of 99%, respectively 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 prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate to the desired level with water containing emulsifier Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with larvae of the horseradish leaf beetle (Phaedon cochleariae) occupied 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 were killed.

This test shows at an exemplary active ingredient concentration of 500 ppm z. B. 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 preparation examples after 7 days one 100% kill.

Example G Plutella Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate to the desired level with water containing emulsifier Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation of the desired concentration and treated with caterpillars (Plutella xylostella) as long as 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 are killed were.

This test shows at an exemplary drug concentration of 500 ppm z. B. the compound 7 of the manufacturing examples after 7 days a kill of 100%.

Example H Spodoptera exigua test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate to the desired level with water containing emulsifier Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars of the army worm (Spodoptera exigua) occupied 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 are killed were.

This test shows at an exemplary drug concentration of 500 ppm z. B. the compound 7 of the manufacturing examples after 7 days a kill of 100%.

Example I Spodoptera frugiperda test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water containing emulsifier to the desired level Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars of the army worm (Spodoptera frugiperda) occupied 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 are killed were.

This test shows at an exemplary active ingredient concentration of 500 ppm z. B. 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 7 days a kill of 100%.

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 prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate to the desired level with water containing emulsifier Concentration.

Bean plants (Phaseolus vulgaris), strongly of all stages of the common Spider mite (Tetranychus urticae) are infested in an active ingredient preparation 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 were killed.

This test shows at an exemplary drug concentration of 100 ppm z. B. the compound 19 of the manufacturing examples 95% kill and the Compound 34 of the preparation examples 100% kill, after 7 days in each case.

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 prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water to the desired one Concentration.

Soybean shoots (Glycine max) of the Roundup Ready variety (trademark of Monsanto Comp. USA) are the desired by diving into the active ingredient preparation Treated with concentration and filled with the tobacco bud caterpillar Heliothis virescens, as long as the leaves are still damp.

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

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 prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the specified amount of solvent gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

The active ingredient preparation is poured onto the floor. The plays Concentration of the active ingredient in the preparation practically no role, is crucial only the amount of active substance per unit volume of soil, which is in ppm (mg / l) is given. The bottom is filled into 0.25 l pots and left at 20 ° C stand.

Immediately after the preparation, 5 pre-germinated maize kernels of the YIELD 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 another 7 The effectiveness of the active ingredient is measured by counting the accumulated days Corn plants determined (1 plant = 20% effect).

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 prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

Young plants are tested with the Active ingredient preparation sprayed in the application rate specified. After the The plants are sprayed with an aqueous spore suspension of Powdery mildew pathogen Podosphaera leucotricha inoculated. The plants are then in the Greenhouse set up at approx. 23 ° C and a relative humidity of approx. 70%.

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

In this test, at an exemplary application rate of 100 g / ha. B. the Compounds 3, 9, 11, 13, 24, 26, 31, 32 and 34 of the preparation examples one 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 prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

Young plants are tested with the Active ingredient preparation sprayed in the application rate specified. To The plants dry with a watery conidia suspension of the apple scab pathogen Venturia inaequalis and then remain for 1 day approx. 20 ° C and 100% relative humidity in an incubation cabin.

The plants are then in a greenhouse at about 21 ° C and a relative Air humidity of approx. 90% set up.

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

In this test, at an exemplary application rate of 100 g / ha. B. the Compounds 3, 9, 11, 13, 24, 26, 31, 32 and 34 of the preparation examples one 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 prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young cucumber plants are sprayed with the Active ingredient preparation in the specified application rate. 1 day after the The plants are treated with a spore suspension of Sphaerotheca fuliginea inoculated. The plants are then grown in a greenhouse at 70% relative humidity and a temperature of 23 ° C.

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

In this test, at an exemplary application rate of 750 g / ha. B. the Compounds 6, 9, 13 and 21 of the preparation examples have 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 prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

Young plants are tested with the Active ingredient preparation sprayed in the application rate specified. After the The plants are sprayed with a conidia suspension of Puccinia recondita sprayed. The plants remain at 20 ° C and 100% relative for 48 hours Humidity in an incubation cabin.

The plants are then grown in a greenhouse at a temperature of approximately 20 ° C and a relative humidity of 80% set up to the development of Favor rust pustules.

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

In this test show at an exemplary application rate of 500 g / ha. B. the Compounds 1 and 3 of the preparation examples have an efficiency of 100%.

Claims (11)

1. 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 represents halogen, alkyl or haloalkyl and
p stands for 0, 1 or 2. 2. Substituted 4-aminopyridine derivatives of the formula (I) according to Claim 1, in which
R ^{1 represents} C ₁ -C 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:
Halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, cyano, nitro, formyl, hydroxyimino, alkoxyimino, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, optionally substituted phenyl, optionally substituted morpholino or optionally substituted tetrazolyl,
n represents 1 or 2,
Y for fluorine, chlorine, bromine; C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl,
p stands for 0, 1 or 2. 3. Substituted 4-aminopyridine derivatives of the formula (I) according to Claim 1, in which
R ^{1 represents} C ₁ -C ₂ 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 particular substitution options), the same or different, 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; each C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ alkylthio which are mono- to quintuple, identical or different, substituted by fluorine or chlorine; Cyano, nitro, formyl, hydroxyimino, C ₁ -C ₄ alkoxyimino, C ₁ -C ₄ alkylcarbonyl, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkoxycarbonyl-C ₁ -C ₄ alkyl; phenyl optionally substituted 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; 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 C ₁ -C ₄ -alkyl,
n represents 1 or 2,
Y represents fluorine, chlorine, methyl or trifluoromethyl,
p stands for 0, 1 or 2. 4. Substituted 4-aminopyridine derivatives of the formula (I) according to Claim 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, which can each be monosubstituted to trisubstituted (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; Methoxycarbonylmethyl, 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. 5. A 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 (II)


in which
R ¹ and R ^{2 have} the meanings given in Claim 1,
and phenylacetic acids of the formula (III)


in which
Het, Y, n and p have the meanings given in claim 1, 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 catalyst activating the carboxyl group and in the presence of a diluent; or a) substituted 4-aminopyridines of the formula (IV)


in which
R ¹ and R ^{2 have} the meanings given in claim 1 and
Q represents a leaving group,
with bromides of the formula (V)


in which
Het, Y and p have the meanings given in claim 1 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 a) substituted 4-aminopyridines of the formula (VI)


in which
R ¹ and R ^{2 have} the meanings given in claim 1, with compounds of the formula (VII)


in which
Het, Y and p have the meanings given in claim 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. Pesticides and / or unwanted agents Microorganisms, characterized in that they contain at least one compound of formula (I) according to claim 1 in addition to extenders and / or surfactants. 7. Use of compounds of formula (I) according to claim 1 for Control of pests and / or unwanted microorganisms. 8. Procedures for pest and / or unwanted control Microorganisms, characterized in that compounds of the formula (I) according to claim 1 to pests and / or microorganisms and / or their lets each habitat act. 9. Process for the preparation of pest control agents and / or undesirable microorganisms, characterized in that compounds of formula (I) according to claim 1 with extenders and / or surface-active substances mixed. 10. phenylacetic acids of the formula (III)


in which
Het, Y, n and p have the meanings given in Claim 1. 11. Substituted 4-aminopyridines of the formula (IV)


in which
R ¹ and R ^{2 have} the meanings given in claim 1 and
Q stands for a leaving group.