WO1997028133A1 - Acylated 4-amino- and 4-hydrazinopyrimidines and their use as pesticides - Google Patents

Abstract

The invention relates to novel compounds of formula (I) in which R1, R2, Ar, A and X have the meanings indicated in the description, and to methods of producing said compounds and their use in combating pests and as fungicides.

Description

 ACYLATED 4-AMINO AND 4-HYDRAZINOPYRIMIDINE AND THEIR USE AS A PEST CONTROL.

The invention relates to new 4-amino and 4-hydrazinopyrimidines, processes for their preparation and their use for controlling animal pests and as fungicides.

It is already known that certain acylated 4-aminopyrimidine derivatives have insecticidal properties (cf. WO-A 95/18 795)

The level and / or duration of action of these previously known compounds is, however, not completely satisfactory in all areas of application, in particular against certain organisms or at low application concentrations

New 4-amino and 4-hydrazinopyrimidines of the formula (I) have been found

in which R ¹ and R ^{2 are} independently hydrogen, halogen, nitro, cyano alkyl

Haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkow alkyl, alkylthio, alkylsulfinyl, alkyl sulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, amino, alkylamino, dialkylamino, aminocarbonyl, alkylaminocarbonyl for dialkylaminocylyl, optionally substituted for alkyl, alkylaminothylyl substituted phenyl, where at least one of the substituents R ¹ and R ^{2 is} different from hydrogen, or R ¹ and R ² together with the carbon atoms to which they are attached represent an optionally substituted, saturated or unsaturated ring which optionally contains one or more heteroatoms,

A represents -NR ³ - or -NR ³ -NR ⁴ -, where R ³ and R ⁴ independently of one another represent hydrogen, alkyl, alkoxyalkyl,

Are alkylcarbonyl or in each case optionally substituted aryl or arylcarbonyl,

X represents oxygen or sulfur,

Y stands for a direct bond, in each case optionally substituted alkylidene, alkylideneoxy and alkylidethio or for alkenylidene and

Ar represents optionally substituted aryl or optionally substituted hetaryl.

It has also been found that the new acylated 4-amino- and 4-hydrazinopyrimidines of the formula (I) are obtained if a) pyrimidine derivatives of the formula (II)

 in which

A, R ¹ and R ^{2 have} the meaning given above, with acid halides of the formula (III) Hal-CO-Y-Ar (III) in which Y and Ar have the meaning given above and

Hai represents halogen, in the presence of a base and in the presence of a diluent, and optionally b) the 4-amino- and 4-hydrazinopyrimidines of the formula (Ia) thus obtained

 in which

A, R ¹ , R ² , Y and Ar have the meaning given above, with a sulfurizing agent, if appropriate in the presence of a diluent

Furthermore, it was found that the new acylated 4-amino- and 4-hydrazinopyrimidines of the formula (I) are very good as fungicides and for controlling animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forests and in stock - and material protection as well as on the

Hygiene sector occur, are suitable

Surprisingly, the acylated 4-amino- and 4-hydrazinopyrimidines of the formula (I) according to the invention show a considerably better activity against animal pests than the constitutionally similar known compounds. The compounds according to the invention are generally defined by the formula (I) Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below.

R ¹ and R ² independently of one another preferably represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₆ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ - C ₄ -haloalkoxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkoxy-C ₁ - C ₄ -alkyl, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ - Alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ - C ₂ haloalkylthio, C ₁ -C ₂ haloalkylsulfinyl, C ₁ -C ₂ haloalkylsulfonyl, amino, C ₁ -C ₄ alkylamino, di (C ₁ -C _4- alkyl) amino, aminocarbonyl, C ₁ -C ₄ -alkylaminocarbonyl, di (C ₁ -C ₄ -alkyl) aminocarbonyl, aminothiocarbonyl, C ₁ -C ₄ -alkylaminothiocarbonyl, di (C ₁ -C ₄ -alkyl) aminothiocarbonyl, for optionally monosubstituted to trisubstituted, identically or differently, by halogen or C ₁ -C ₄ alkyl-substituted C ₃ -C ₆ -cycloalkyl or for optionally monosubstituted to trisubstituted, identically or differently, phenyl, the substituents being halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ - C ₄ alkylthio, C ₁ -C ₄ Haloalkyl, C ₁ -C ₄ haloalkoxy and C ₁ -C ₄ -

Haloalkylthio come into question, wherein at least one of the substituents R ¹ and R ^{2 is} different from hydrogen or

R ¹ and R ² , together with the carbon atoms to which they are attached, preferably represent an optionally single to triple, identical or different, halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy , C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ haloalkylthio substituted, saturated or unsaturated 5- or 6-membered ring, which has 1 or 2 heteroatoms , such as N, O or S atoms

A preferably represents -NR ³ - or -NR ³ -NR ⁴ -, wherein

R ³ and R ⁴ independently of one another for hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkylcarbonyl or for in each case optionally up to three times the same or different halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ -haloalkoxy or C ₁ -C ₄ haloalkylthio substituted phenyl or phenylcarbonyl X preferably represents oxygen or sulfur.

Y preferably stands for a direct bond, in each case optionally through

Halogen or C ₃ -C ₆ cycloalkyl substituted C ₁ -C ₆ alkylidene, C ₁ -C ₆ alkylideneoxy or C ₁ -C ₆ alkylidethio or for C ₂ -C ₆ alkenylidene. Ar preferably represents phenyl which is monosubstituted to trisubstituted by identical or different substituents, the following being suitable as substituents: halogen, nitro, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ - Alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ haloalkylthio and each optionally mono- to trisubstituted, identically or differently substituted, phenyl, phenoxy, phenylthio, benzyl, pyridinyloxy, pyrimidinyloxy, thiazolyloxy or Thiadiazolyloxy, where the following are suitable as substituents:

Halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ - C ₄ haloalkyl, C ₁ -C ₄ -haloalkoxy, C ₁ -C ₄ -haloalkylthio;

for a condensed bi- or tricyclic radical which is optionally monosubstituted to fivefold, identical or different, substituted by halogen, nitro, cyano or C ₁ -C ₄ -alkyl and also contains one or more heteroatoms, such as O, S or N atoms can or for optionally mono- to trisubstituted, identically or differently substituted 5- or 6-membered hetaryl with 1 to 3 heteroatoms. such as N, S and O atoms, the following being suitable as substituents:

Halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ - C ₄ haloalkyl, C ₁ -C ₄ -haloalkoxy and C ₁ -C ₄ haloalkylthio.

R ¹ and R ² independently of one another particularly preferably represent hydrogen, chlorine, bromine, nitro, cyano, methyl, ethyl, chloromethyl, trifluoromethyl,

Methoxy, ethoxy, trifluoromethoxy, methoxymethyl, ethoxymethyl, trifluoromethoxymethyl, methylthio, methyl sulfinyl, methyl sulfonyl, amino, methylamino, dimethylamino, aminocarbonyl, aminothiocarbonyl;

 for in each case optionally single or double, identical or different, substituted by fluorine, chlorine, bromine, methyl or ethyl, cyclopropyl,

Cyclopentyl or cyclohexyl;

or for phenyl which is monosubstituted to trisubstituted identically or differently, where fluorine, chlorine, bromine, nitro, Cyano, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy and trifluoromethylthio come into question, where at least one of the substituents R ¹ and R ^{2 is} different from hydrogen or R ¹ and R ² are together with the carbon atoms to which they are attached are particularly preferred for phenyl, pyrazolyl, imidazolyl or thiazolyl which are each substituted once or twice, identically or differently, by fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio. A particularly preferably represents -NR ³ - or -NR ³ -NR ⁴ -, wherein

R ³ and R ⁴ independently of one another represent hydrogen, methyl, ethyl, methoxymethyl, ethoxymethyl, ethoxyethyl, acetyl or optionally phenylcarbonyl which is substituted once or twice, identically or differently, by fluorine, chlorine, nitro, cyano, methyl or trifluoromethyl.

X particularly preferably represents oxygen or sulfur.

Y particularly preferably represents a direct bond or one of the groups -CH ₂ -, -CH (CH ₃ ) -, -CH (C ₂ H ₅ ) -, -CH (C ₃ H ₇ -i) -, -CH ₂ CH ₂ -, -CH ₂ O-, - CH ₂ S- or -CH = CH-. Ar particularly preferably represents phenyl which is monosubstituted to trisubstituted identically or differently, the following being suitable as substituents:

 Fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio , Difluoromethylthio and in each case optionally monosubstituted to trisubstituted, identically or differently substituted, phenyl, phenoxy, pyridinyloxy, pyrimidinyloxy, thiazolyloxy or thiadiazolyloxy, the following being suitable as substituents:

Fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, difluoromethyl _, Trifluoromethoxy, difluoromethoxy, trifluoromethylthio and difluoromethylthio;

 for one of the bi- or tricyclic radicals

 which are optionally substituted once to five times (preferably once to three times, in particular once or twice), identically or differently, by fluorine, chlorine, bromine, nitro, cyano, methyl or ethyl; or for one of the heteroaromatics of the formulas

 which are optionally monosubstituted to trisubstituted (preferably monosubstituted or disubstituted), substituted identically or differently by fluorine, chlorine, nitro, cyano, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethyithio.

The hydrocarbon radicals mentioned above in the definition of the compounds according to the invention, such as alkyl, can also be used in connection with heteroatoms such as

Alkoxy - if possible, be straight-chain or branched

The general definitions or explanations of residues or explanations listed above or in preferred areas can be combined with one another, that is to say also between the respective areas and preferred areas. They apply accordingly to the end products as well as to the preliminary and intermediate products.

According to the invention, preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as preferred (preferred) According to the invention, particular preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as being particularly preferred.

Compounds of the general formulas (IA) to (ID) are particularly preferred

in which

Y and Ar represent the general, preferred and particularly preferred meanings mentioned above.

In addition to the preparation examples, the compounds listed in the following table may be mentioned as examples:

If, for example, 4-amino-5-chloro-6-ethyl-pyrimidine and 4-bromophenylacetyl chloride are used as starting materials in process (a), the course of the process according to the invention can be represented by the following reaction scheme:

 If, for example, N- (5-chloro-6-ethyl-4-pyrimidyl) -4- (4-nitrophenoxy) phenylacetamide is used as starting material and Lawesson's reagent (2,4-bis- (4-methoxyphenyl ) -l, 3-dithia-2,4-diphosphetane-2,4-disulfide) as a sulfurizing agent, the course of the process according to the invention can be represented by the following reaction scheme:

Formula (II) provides a general definition of the pyrimidine derivatives required as starting materials for carrying out process (a) according to the invention. In formula (II), A, R and R preferably or particularly preferably have those meanings which are preferred or particularly preferred for these in connection with the description of the compounds of formula (I)

Substituents were called.

Some of the pyrimidine derivatives of the formula (II) are known (cf., for example, Rasmussen, van der Pias, Recl. Trav. Chim. Pays-Bas 97, 288 (1978); J. Heterocycl. Chem. 28 (5), 1357 (1991)) or they can be obtained in a known manner (cf. also the following information on the preparation of new pyrimidine derivatives of the formula (Ha)).

Not yet known and also the subject of this application are the pyrimidine derivatives of the formula (IIa)

in which

A has the meaning given above.

The new pyrimidine derivatives of the formula (IIa) are obtained, for example, by the 4,5-dichloro-6-ethylpyrimidine of the formula (IV)

with amines or hydrazines of the formula (V)

HAH (V) in which A has the meaning given above, in the presence of a base and optionally in the presence of a diluent.

All customary solvents can be used as diluents. Halogenated aliphatic or aromatic hydrocarbons, ethers or nitriles, such as e.g. Cyclohexane, toluene, chlorobenzene, chloroform, dichloromethane, dichloroethane, dioxane, tetrahydrofuran, diethyl ether or acetonitrile.

However, it is also possible to work in the melt without a diluent. The method described above for the preparation of the compounds of formula

(IIa) is carried out in the presence of a base.

All common proton acceptors can be used as bases. Alkali or alkaline earth metal hydroxides, alkali or alkaline earth metal carbonates or hydrogen carbonates or nitrogen bases are preferably usable. Examples include sodium hydroxide, calcium hydroxide, potassium carbonate, sodium hydrogen carbonate, triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoiin, diazabicyclooctane (DABCO), diazabicyclonones (DBN) and diazabicycloundecene (DBU).

A corresponding excess of amine or hydrazine of the formula (V) can preferably also be used.

The reaction temperatures can be varied over a wide range. In general, temperatures between -40 ° C and + 200 ° C, preferably between 0 ° C and 150 ° C.

In some cases it can be beneficial to work under increased pressure.

When carrying out the process described above for preparing the compounds of the formula (IIa), 4,5-dichloro-6-ethyl is generally employed per mole pyrimidine of the formula (IV) 1 to 3 mol, preferably 1 to 2 mol of amine or hydrazine of the formula (V).

The compounds of the formula (Ha) are worked up and isolated in a generally known manner. 4,5-dichloro-6-ethylpyrimidine of the formula (IV) is known (cf. EP-A 0 370 391).

The amines or hydrazines of the formula (V) are generally known compounds of organic chemistry

Formula (III) provides a general definition of the acid halides required as starting materials for carrying out process (a) according to the invention. In the formula (III), Y and Ar preferably or particularly preferably have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) or particularly preferably for these substituents.

Shark is preferably chlorine or bromine. The acid halides of the formula (III) are generally known compounds of organic chemistry.

The starting materials of the formula (Ia) used in the production process (b) are compounds according to the invention and can be obtained in accordance with the information from the production process (a). Suitable diluents for carrying out process (a) according to the invention are all customary solvents. Halogenated aliphatic or aromatic hydrocarbons, ethers or nitriles such as, for example, cyclohexane, toluene, chlorobenzene, chloroform, dichloromethane, dichloroethane, dioxane, tetrahydrofuran, diethyl ether or acetonitrile are preferably usable However, it is also possible to work in the melt without a solvent

Process (a) described above for the preparation of the compounds of the formula (I) is carried out in the presence of a base All conventional proton acceptors can be used as bases in process (a). Alkali or alkaline earth metal hydroxides, alkali or alkaline earth metal carbonates or hydrogen carbonates or nitrogen bases are preferably usable. Examples include sodium hydroxide, calcium hydroxide, potassium carbonate, sodium hydrogen carbonate, triethylamine, dibenzylamine, diisopropylamine, pyridine,

Quinoline, diazabicyclooctane (DABCO), diazabicyclonones (DBN) and diazabicycloundecene (DBU).

A corresponding excess of pyrimidine derivative of the formula (II) can preferably also be used. The reaction temperatures can be varied within a wide range in process (a) described above. In general, temperatures between -40 ° C and + 200 ° C, preferably between 0 ° C and 100 ° C.

When carrying out process (a) described above for the preparation of the compounds of the formula (I), 0.1 to 2 mol, preferably 0.4 to 1.5 mol, are generally employed per mol of pyrimidine derivative of the formula (II) Acid shark ogenid the

Formula (III).

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

Possible sulfurizing agents in carrying out process (b) according to the invention are: phosphorus pentasulfide or Lawesson's reagent [2,4-bis (4-methoxyphenyl) -1,3,2,4-dithiadiphosphetane-2,4-dithione] ( see also Tetrahedron Vol. 41, No. 22, 5061 ff (1985))

Suitable diluents for carrying out process (b) according to the invention are preferably hydrocarbons, such as toluene, xylene, tetralin, hexane or cyclohexane.

The reaction temperatures can be varied within a substantial range in carrying out process (b) according to the invention. In general, temperatures between 0 ° C. and 200 ° C., preferably between 20 ° C. and 150 ° C. When carrying out process (b) according to the invention, generally between 1 and 3 mol, preferably between 1 and 2 mol, of sulfurizing agent are used per mol of compound of the formula (Ia). The processing takes place according to usual methods. In some cases it may prove advantageous to directly combine the pyrimidine derivatives of the formula (II) with halides of the formula (purple)

Hal-CS-Y-Ar (IIIa) in which

Shark, Y and Ar have the meaning given above to implement under the conditions of process a) described above.

With good plant tolerance and favorable warmth toxicity, the active ingredients are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stocks 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 e.g. Oniscus asellus, Armadillidium vulgare, Porcelli o scaber. From the order of the Diplopoda e.g. Blaniulus guttulatus.

From the order of the Chilopoda e.g. Geophilus carpophagus, Scutigera spec.

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

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

From the order of the Collembola, for example Onychiurus armatus. From the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

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

From the order of the anoplura e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci. From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius,

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

From the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigususpp. Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus s. _: Psylla spp

From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Agristella sppber, Bucculisellappl ., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomoneila, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestellaellaolaelliellellae, Tellaellaellae, Tella , Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana. From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Lepünotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrisoamisilamisppas, Atomic spp. Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Niptus holium ps spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera e.g. Diprion spp, Hoplocampa spp, Lasius spp, Monom orium pharaonis, Vespa spp

From the order of Diptera, for example Aedes spp, Anopheles spp, Culex spp, Drosophila melanogaster, Musca spp, Fannia spp, Calliphora erythrocephala, Lucilia spp, Chrysomyia spp, Cuterebra spp, Gastrophilus spp., Hyppobosca spp,

Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp, Bibio hortulanus, Oscmella frit, Phorbia spp, Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp From the order of the Arachnida, for example Scorpio maurus, Latrodectus mactans

From the order of the Acarina, for example Acarus siro, Argas spp, Ornithodoros spp, Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp, Rhipicephalus spp., Amblyomma spp, Hyalomma spp, Ixodes spp., Psoroptes spp., Psoroptes spp , Tarsonemus spp, Bryobia praetiosa, Panonychus spp, Tetranychus spp

Plant parasitic nematodes include, for example, Pratylenchus spp, Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp, Globodera spp., Meloidogyne spp, Aphelenchoides spp, Longidorus spp, Xiphinema spp, Trichodor The compounds of the formula (I) according to the invention are notable in particular for outstanding insecticidal activity. They can be used with particularly good success in combating plant-damaging insects.

They show strong effects, for example, against horseradish leaf beetle larvae (Phaedon cochleariae), caterpillars of the cockroach (Plutella maculipennis), caterpillars of the owl butterfly (Spodoptera frugiperda), the peach aphid (Mycus persicae) and against the green leafhopper (Nephotpsettix cinctice).

The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents

Agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. Liquid solvents are essentially suitable. Aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol 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.

The following are suitable as solid carriers:

Eg ammonium salts and natural rock flour, such as kaolins, clays. Talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Suitable emulsifying and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene

Fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

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

Dyes such as inorganic pigments, for example 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% by weight of active compound, preferably between 0.5 and 90%. The active compound according to the invention can be used in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active compounds, such as insecticides and attractants , Sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides are present. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons,

Phenylureas, substances produced by microorganisms u. a.

Particularly cheap mixing partners are e.g. the following:

Fungicides:

2-aminobutane, 2-anilino-4-methyl-6-cyclopropyl-pyrimidine, 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazole-5- carboxanilide, 2,6-di chloroN- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,

Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,

Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,

Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,

Edifenphos, Epoxyconazole, Ethirimol, Etridiazol, Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin,

Fenpropimorph, Fentin Acetate, Fentin Hydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, Folpet, Fosetyl-Aluminum, Fthalide, Fuberidazol, Furalaxyl, Guazecatine

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,

Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil, Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, oxadixyl, oxamocarb, oxycarboxin,

Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,

Quintozen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, Tecloftalam, Tecnazen, Tetraconazole, Thiabendazole, Thicyofen, Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Trifluminol, Trifluminol

Triticonazole,

Validamycin A, vinclozolin,

Zineb, ziram

Bactericides: bronopol, dichlorophene, nitrapyrin, nickel-dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarbacytututhrin, Bensultap

Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin,

Clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,

Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,

Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox,

Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos,

Methami dophos, methidathione, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, Naled, NC 184, NI 25, Nitenpyram

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos,

Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,

Quinalphos,

RH 5992,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos,

Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb,

Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin. A mixture with other known active ingredients, such as herbicides or with

Fertilizers and growth regulators are possible.

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

The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight. The application takes place in a customary manner adapted to the application forms.

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

The active compounds according to the invention act not only against plant, hygiene and stored-product pests, 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 e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the subordinates Amblycerina and Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp ..

From the order Diptera and the subordinates Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota ., 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, for example Pulex spp., Ctenocephalides spp,

Xenopsylla spp., Ceratophyllus spp ..

From the order of the Heteropterida, for example Cimex spp., Triatoma spp. Rhodnius spp., Panstrongylus spp .. From the order of the Blattarida, for example Blatta orientaüs, Periplaneta americana, Blattela germanica, Supella spp ..

From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata e.g. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,

Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp ..

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Omithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectolich spp., Pod ., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..

The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, e.g. Cattle, sheep,

Goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, house birds, aquarium fish and so-called experimental animals, such as Infest hamsters, guinea pigs, rats and mice. Combating these arthropods is said to result in deaths and reduced performance (in meat, milk, wool, skins, eggs,

Honey, etc.) can be reduced, so that more economical and simple animal husbandry is possible through the use of the active compounds according to the invention.

The active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, of feed-through

Method, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), Pouring on (pour-on and spot-on), washing, powdering and with the help of active ingredients

Shaped bodies, such as collars, ear tags, tail tags, limb straps, holsters, marking devices, etc. When used for cattle, poultry, pets, etc., the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or apply after 100 to 10,000-fold dilution or use it as a chemical bath.

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

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

Beetle like

 Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces rug, Lyctus pubescescis, Lyctus pubis linearis, Lyctus pubes linearis, Lyctus pubis Xyleborus spec.

Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus

Skin wings like

 Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur termites such as

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

Bristle tails, such as Lepisma saccarina. In the present context, technical materials include non-living ones

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

The material to be protected against insect infestation is very particularly preferably wood and wood processing products. Wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are to be understood as examples: timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone masts, wooden cladding, wooden windows and doors , Plywood, chipboard, carpentry or wood products that are used in general in house construction or joinery.

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

The formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellent, optionally siccatives and UV stabilizers and optionally dyes and pigments and further processing aids.

The insecticidal compositions or concentrates used to protect wood and wood-based materials 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 occurrence of the insects and on the medium. The optimum amount to be used can be determined in each case by use of test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected

An organic-chemical solvent or solvent mixture and / or an oily or oil-like semi-volatile organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or water and / or water and optionally one serves as solvent and / or diluent Emulsifier and / or wetting agent

The organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C. Water-insoluble, oily and oil-like solvents are used corresponding mineralols or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene.

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

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

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

In the context of the present invention, the known organic-chemical binders are the water-dilutable synthetic resins and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, e.g. Polyvinyl acetate,

Polyester resin, polycondensation or poly addition 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 are used.

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

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

All or part of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent the active ingredients from cursing and from crystallizing or precipitating. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

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

Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvmylmethylether 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 by industrial impregnation processes, e.g. vacuum, double vacuum or pressure processes.

The ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides. The insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional admixing partners. The compounds mentioned in this document are an integral part of the present application.

Insecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, decamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, triflumurone, and epizazole, as well as fungizazone, such as epizazole, such as epizazole, as well as fungizazone, such as epizazole, such as epizazole, such as epizazole, as well as fungizazone, such as epizazole, as Cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propynyl-butylcarbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one. The active compounds according to the invention also have a strong microbicidal action and can be used practically to combat unwanted microorganisms. The active ingredients are suitable for use as crop protection agents, in particular as fungicides.

Fungicidal agents in crop protection are used to combat Piasmodi ophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Bactericidal agents are used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae. 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 fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil. They can be used, for example, with particularly good success against the pathogen of apple mildew (Podosphaera leucotricha) and apple scab (Venturia inaequalis).

In addition, they also have a good effect against diseases in fruit and vegetable growing, such as against the pathogen of the wrong vine mildew (Plasmopara viticola) or the tomato brown rot (Phytophthora infestans), as well as against the rice stain disease (Pyricularia oryzae).

When used as fungicides, the active compounds according to the invention can be used as such, in the form of their commercially available formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusting agents and granules. The application is carried out in the customary manner, e.g. by pouring, spraying, atomizing, scattering, foaming, brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient itself into the soil. It can also be

Seeds of the plants are treated.

When treating parts of plants, the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

In the seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.

The preparation and use of the active compounds according to the invention can be seen from the examples below. Production Examples Example 1

 2.26 g (9.7 mmol) are added dropwise at room temperature to a solution of 3.05 g (19.4 mmol) of 4-amino-5-chloro-6-ethyl-pyrimidine (Ila-1) in 30 ml of tetrahydrofuran. 4¬

Bromophenylacetyl chloride and stirred for 16 hours at room temperature.

For working up, the solid is filtered off with suction, the filtrate is concentrated and the residue is partitioned between dichloromethane and water, the org. Phase dried and concentrated. When the crude product is triturated with a little ether, the product is obtained in the form of a solid.

1.80 g (52% of theory) of N- (5-chloro-6-ethyl-4-pyrimidyl) -4-bromophenylacetamide with a melting point of 150-152 ° C. are obtained.

Manufacture of the starting product

10 g (56 mmol) of 4,5-dichloro-6-ethyl-pyrimidine are concentrated in 200 ml

Ammonia water stirred for 8 hours at 150 ° C in an autoclave. The precipitated solid is filtered off and dried.

7.0 g (78% of theory) of 4-amino-5-chloro-6-ethyl-pyrimidine with a melting point of 136-137 ° C. are obtained. Example 2

 A solution of 1.58 g (10 mmol) of 4-amino-5-chloro-6-ethyl-pyrimidine (IIa-1) and 0.95 g (12 mmol) of pyridine in 50 ml of dichloromethane is added dropwise at 0-10 ° C 3.26 g (12 mmol) 4- (4-cyano-phenoxy) -phenylacetyl chloride and stirred for 16 hours

Room temperature.

For working up, the reaction mixture is washed with dilute hydrochloric acid, water, dried and evaporated.

3.66 g (93% of theory) of N- (5-chloro-6-ethyl-4-pyrimidyl) -4- (4-cyanophenoxy) phenylacetamide with a melting point of 77-80 ° C. are obtained.

Example 3

 To a solution of 3.73 (20 mmol) N- (5-chloro-6-ethyl-4-pyrimidyl) -N-methylhydrazine (IIa-2), 2.02 g (20 mmol) triethylamine and a spatula tip of diazabicyclooctane ( DABCO) in 50 ml of tetrahydrofuran is added dropwise at 0-10 ° C. 4.21 g

(20 mmol) 4-tert-butyl-phenylacetyl chloride and stirred for 16 hours at room temperature.

For working up, the mixture is concentrated, the residue is partitioned between methylene chloride and water and the organic phase is dried and concentrated. 6.55 g (91% of theory) of N '- (5-chloro-6-ethyl-4-pyrimidyl) -N'-methyl¬ are obtained

N-4-tert-Butyl-phenylacetic acid hydrazide (A = NCH ₃ -NH) from the melting point Manufacture of the starting product

 9.20 g (200 mmol) of methylhydrazine are added dropwise to a solution of 17.7 g (100 mmol) of 4,5-dichloro-6-ethyl-pyrimidine in 150 ml of acetonitrile at 0 ° C. and the mixture is stirred at room temperature for 16 hours.

For working up, the solid is suctioned off and the filtrate is evaporated.

19.2 g (100% of theory) of N- (5-chloro-6-ethyl-4-pyrimidyl) -N-methylhydrazine are obtained as orange oil. ¹ H NMR (CDCl ₃ ): 1.28 (t, 3H), 2.87 (q, 2H), 3.37 (s, 3H), 4.5 (br, 2H), 8.49 (s , 1H) ppm.

Example 4

 3.59 g (20 mmol) of 4-amino-5-chloro-quinazoline are placed in 50 ml of tetrahydrofuran, 1.89 g (10 mmol) of 4-chlorophenyl acetyl chloride are added and the mixture is heated under reflux for 16 hours. For working up, the solid is filtered off with suction, the filtrate is concentrated and the

Distributed residue between dichloromethane and water, the organic phase dried and evaporated. When the crude product is triturated with a little ether, the product is obtained in the form of a solid.

1.30 g (40% of theory) of 4- (4-chlorophenyl-acetylamino) -5-chloroquinazoline with a melting point of 150-152 ° C. are obtained. Example 5

 4.0 g (30 mmol) of adenine are placed in 20 ml of pyridine, 24.1 g (90 mmol) of (4-cyano-phenoxy-4-phenyl-acetyl chloride are added and the mixture is heated under reflux for 3 hours.

For working up, the mixture is concentrated, the residue is partitioned between warm sodium bicarbonate solution and chloroform, the product is filtered off and recrystallized from ethanol.

8.9 g (80% of theory) of N- (4-cyano-phenoxy-4-phenyl-acetyl) adenine with a melting point of 251-255 ° C. are obtained.

Example 6

 0.40 g (0.97 mmol) N- (5-chloro-6-ethyl-4-pyrimidyl) -4- (4-nitro-phenoxy) phenylacetamide and 0.39 g (0.97 mmol) Lawessons- The reagent is refluxed in 10 ml of toluene for 16 hours. For working up, the mixture is concentrated and the product is isolated by column chromatography.

0.08 g (19% of theory) of N- (5-chloro-6-ethyl-4-pyrimidyl) -4- (4-nitrophenoxy) phenylthioacetamide with a melting point of 102-104 ° C. is obtained. The following compounds of the formula (I) were obtained analogously to Preparation Examples 1 to 6 or according to the general instructions for the preparation:

Examples of use

Example A

Phaedon larval test solvent 7 parts by weight of dimethylformamide

Emulsifier. 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration. Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound at the desired concentration and with horseradish leaf beetle larvae (Phaedon cochleariae) occupied while the leaves are still moist

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

In this test, for example, the compounds according to Preparation Examples 8, 10, 13, 23, 24, 30, 35, 43, 52, 62, 71 and 74 caused a death rate of 100% according to FIG. 7 at an exemplary active ingredient concentration of 0.1% Days

Example B

PIutella test

Solvent: 7 parts by weight of dimethylfomamide

 Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by dipping into the active ingredient preparation of the desired concentration and with caterpillars of the cabbage cockroach

(Plutella maculipennis) occupied while the leaves are still moist.

After the desired time, the death rate is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed. In this test, e.g. the compounds according to the preparation examples

10, 13, 30, 43, 49, 52, 62, 63, 71 and 74 with an exemplary active ingredient concentration of 0.1%, a death rate of 100% after 7 days.

Example C

Spodoptera Frugiperda test

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 stated amount of solvent and the stated amount of emulsifier and dilute the concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by dipping into the active ingredient preparation of the desired concentration and with caterpillars of the owl butterfly

(Spodoptera frugiperda) occupied while the leaves are still moist.

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

In this test, for example, the compounds according to Preparation Examples 13, 24, 42, 43, 47, 62, 67, 69, 71 and 74, with an exemplary active compound concentration of 0.1%, caused 100 deaths after 7 days.

Example D

Myzus test solvent 7 parts by weight of dimethylformamide

 Emulsifier 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Broad bean seedlings (Vicia faba), which are infested with green peach aphids (Myzus persicae), are immersed in the active compound preparation of the desired concentration and placed in a plastic can.

After the desired time, the death rate is determined in percent. 100% means that all aphids have been killed, 0% means that no aphids have been killed. In this test, for example, the compound according to Preparation Example 13 caused a death rate of 90% after 6 days at an exemplary active ingredient concentration of 0.1%.

Example E

Nephotettix test 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 stated amount of solvent and the stated amount of emulsifier and dilute the concentrate with water to the desired concentration.

Rice seedlings (Oryza sativa) are treated by immersing them in the active ingredient preparation of the desired concentration and with larvae of the green rice leafhopper

(Nephotettix cincticeps) occupied while the seedlings are still moist.

After the desired time, the kill is determined in%. 100% means that all cicadas have been killed, 0% means that no cicadas have been killed. In this test, at an exemplary active ingredient concentration of 0.1

% z. B. the compounds according to the preparation examples

47 and 56 a death rate of 80%,

 43 and 44 a death rate of 90%,

 37 a death rate of 95% and

35 and 72 a death rate of 100%, each after 6 days. Example F

Podosphaera test (apple) / protective solvent: 4.7 parts by weight of acetone

 Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the active compound preparation. After the spray coating has dried on, the plants are inoculated by dusting with conidia of the pod mildew pathogen Podosphaera leucotricha.

The plants are then placed in a greenhouse at 23 ° C. and a relative humidity of approx. 70%.

Evaluation is carried out 10 days after the inoculation. This test showed, for example. the compound according to preparation example 52 has an efficiency of 98% at an exemplary active ingredient concentration of 100 ppm.

Example G

Venturia test (apple) / protective

Solvent: 4.7 parts by weight of acetone

 Emulsifier: 0.3 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 plants are sprayed with the active compound preparation. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab pathogen Venturia inaequalis and then remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20 ° C. and a relative humidity of approx. 70%. Evaluation is carried out 12 days after the inoculation.

In this test, e.g. the compound according to preparation example 52 has an efficiency of 99% at an active ingredient concentration of 100 ppm.

Claims

claims

1. Compounds of formula (I)

 in which

R ¹ and R ² independently of one another are hydrogen, halogen, nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, alkylthio, alkylsulfinyl, alkyl sulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, amino, alkylamino, dialkylamino, aminocarbonyl, alkylaminocarbonyl , Dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, represent optionally substituted cycloalkyl or optionally substituted phenyl, at least one of the substituents R ¹ and R ^{2 being} different from hydrogen, or

R ¹ and R ² together with the carbon atoms to which they are attached represent an optionally substituted, saturated or unsaturated ring which optionally contains one or more heteroatoms, represents -NR ³ - or -NR ³ -NR ⁴ -, in which

R ³ and R ⁴ independently of one another represent hydrogen, alkyl, alkoxyalkyl, alkyl carbonyl, or in each case optionally substituted aryl or arylcarbonyl, X represents oxygen or sulfur,

Y stands for a direct bond, in each case optionally substituted alkylidene, alkylideneoxy and alkylidethio or for alkenylidene and Ar stands for optionally substituted aryl or optionally substituted hetaryl.

2. Compounds of formula (I) according to claim 1, in which

R ¹ and R ² independently of one another for hydrogen, fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ - C ₄ - Haloalkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ - Alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₂ haloalkylthio, C ₁ -C ₂ haloalkylsulfinyl, C ₁ -C ₂ haloalkylsulfonyl, amino, C ₁ -C ₄ alkylamino, di (C ₁ -C ₄ -alkyl) amino, aminocarbonyl, C ₁ -C ₄ -alkylaminocarbonyl, di (C ₁ -C ₄ -alkyl) aminocarbonyl, aminothiocarbonyl, C ₁ -C ₄ -

Alkylaminothiocarbonyl, di (C ₁ -C ₄ alkyl) aminothiocarbonvl, for C ₃ -C ₆ cycloalkyl which is optionally monosubstituted to trisubstituted identically or differently by halogen or C ₁ -C ₄ alkyl or for optionally monosubstituted to triple, identical or differently substituted phenyl, where halogen, nitro,

Cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy and C ₁ -C ₄ haloalkylthio in Question come, wherein at least one of the substituents R ¹ and R ^{2 is} different from hydrogen or

R ¹ and R ² together with the carbon atoms to which they are attached represent an optionally single to triple, identical or different, halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ -

Alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ - haloalkoxy or C ₁ -C ₄ -haloalkylthio substituted, saturated or unsaturated 5- or 6-membered ring which may contain 1 to 2 heteroatoms, such as N, O or S atoms,

A stands for -NR ³ - or -NR ³ -NR ⁴ -, where

R ³ and R ⁴ independently of one another for hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkylcarbonyl or for in each case optionally up to three times the same or different halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ or C -HalogenaIkoxy ₁ -C ₄ haloalkylthio substituted phenyl or phenyl carbonyl, X represents oxygen or sulfur,

Y for a direct bond, in each case optionally substituted by halogen or C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkylidene, C ₁ -C ₆ -alkylidoxy or C ₁ -C ₆ -alkylidethio or for C ₂ -C ₆ - Alkenylidene, Ar represents phenyl which is monosubstituted to trisubstituted by identical or different substituents, the following being suitable as substituents: halogen, nitro, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ Alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ haloalkylthio and each optionally mono- to trisubstituted, identically or differently substituted, phenyl, phenoxy, phenylthio,

Benzyl, pyridinyloxy, pyrimidinyloxy, thiazolyloxy or thiadiazolyloxy, where the following are suitable as substituents:

Halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ - haloalkylthio;

for a condensed bi- or tricyclic radical which is optionally monosubstituted to fivefold, identical or different, substituted by halogen, nitro, cyano or C ₁ -C ₄ -alkyl and also contains one or more heteroatoms, such as O, S or N atoms can or represents optionally mono- to trisubstituted, identically or differently substituted 5- or 6-membered hetaryl with 1 to 3 heteroatoms, such as N, S and O atoms, the following being suitable as substituents:

Halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ -

Alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy and C ₁ -C ₄ haloalkylthio.

3. Compounds of formula (I) according to claim 1, in which

R ¹ and R ² independently of one another are hydrogen, chlorine, bromine, nitro, cyano, methyl, ethyl, chloromethyl, trifluoromethyl, methoxy,

Ethoxy, trifluoromethoxy, methoxymethyl, ethoxymethyl, trifluoromethoxymethyl, methylthio, methylsulfinyl, methylsulfonyl, amino, methylamino, dimethylamino, aminocarbonyl, aminothiocarbonyl, for each optionally optionally monosubstituted or disubstituted, identically or differently, by fluorine, chlorine, bromine, methyl or ethyl cyclopentyl propyl or cyclohexyl; or represent optionally monosubstituted to trisubstituted, identically or differently substituted, where substituents fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy and trifluoromethylthio are suitable, at least one of the substituents R ¹ and R ^{2 is} different from hydrogen or

R ¹ and R ² together with the carbon atoms to which they are attached are each substituted, if necessary, once or twice, identically or differently, by fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethyithio Phenyl, pyrazolyl, imidazolyl or thiazolyl, A stands for -NR ³ - or -NR ³ -NR ⁴ -, wherein R ³ and R ⁴ independently of one another are hydrogen, methyl, ethyl, methoxymethyl, ethoxymethyl, ethoxyethyl, acetyl or for phenyl carbonyl optionally substituted once or twice, identically or differently by fluorine, chlorine, nitro, cyano, methyl or trifluoromethyl, for oxygen or sulfur stands for a direct bond or for one of the groups -CH ₂ -, -CH (CH ₃ ) -, -CH (C ₂ H ₅ ) -, -CH (C ₃ H ₇ -i) -, -CH ₂ CH ₂ -, -CH ₂ O- -CH ₂ S- or -CH = CH- represents phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, the following being suitable as substituents: fluorine, chlorine, bromine, nitro, Cyano, methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, difluoromethylthio and in each case, if necessary, single to triple, identical or differently substituted phenyl, phenoxy, pyridinyloxy, pyrimidinyloxy, thiazolyloxy or thiadiaz olyloxy, the following being suitable as substituents:

 Fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio and Difluoromethylthio;

for one of the bi- or tricyclic radicals

which are optionally substituted once to five times (preferably once to three times, in particular once or twice), the same or differently by fluorine, chlorine, bromine, nitro, cyano, methyl or ethyl; or for one of the heteroaromatics of the formulas

stands, which are optionally monosubstituted to trisubstituted (preferably single or double), fluorine, chlorine, nitro, cyano, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.

4. A process for the preparation of compounds of formula (I) according to

Claim 1, characterized in that a) compounds of formula (II)

 in which

A, R ¹ and R ^{2 have} the meaning given in claim 1, with compounds of the formula (III)

Hal-CO-Y-Ar (III) in which Y and Ar have the meaning given in claim 1 and

Hal represents halogen, in the presence of a base and in the presence of a diluent; and if necessary b) the compounds of the formula (Ia) thus obtained

 in which

A, R ¹ , R ² , Y and Ar have the meaning given above, with a sulfurizing agent, if appropriate in the presence of a diluent

5. Compounds of the formula (IIa)

 in which A has the meaning given in claim 1

6. pesticides and fungicidal agents, characterized in that they contain at least one compound of the formula (I) according to claim 1

7. Use of compounds of formula (I) according to claim 1 for controlling pests and fungi.

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

9. A process for the preparation of pesticides and fungicidal agents, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active agents.

10. Use of compounds of formula (I) according to claim 1 for the preparation of pesticides and fungicidal agents.