DE19750402A1 - New pesticidal and fungicidal acylated 4-aminopyridine derivatives - Google Patents

Abstract

2-(1-Oxyalkyl)-4-(N-(hydrocarbyloxycarbonyl)-N-(phenylacetyl)-amino)-p yridine derivatives (I) are new. Pyridine derivatives of formula (I) and their N-oxides and pyridine N-protonated salts are new. Several classes of intermediates are also new. R1 = COY1, COOY2, COSY3, CONH2, CONHY4, CONY5Y6 or SO2Y7; Y1-Y7 = alkyl, haloalkyl, optionally substituted cycloalkyl or optionally substituted phenyl; R2 = H or alkyl; R3 = H, alkyl, halo, CN, CSNH2 or optionally substituted phenyl; R5 = phenyl (optionally substituted, e.g. by 1-4 of halo, alkyl, alkoxy, haloalkyl, haloalkoxy, NO2, CN, CSNH2, alkylthio, alkylsulfinyl and alkylsulfonyl); X = halo, alkyl, alkoxy or haloalkyl; n = 0-3. Independent claims are included for the preparation of (I); and for novel intermediates of formulae (II), (IV), (VI), (IV') and (VI'), including analogues of (II) and (IV) in which R1 is replaced by H.

Description

The present application relates to new acylated 4-aminopyridines, processes for their manufacture and their use for controlling animal pests as well as fungicides.

It is already known that certain substituted 4-aminopyridines insecticidal egg properties (see e.g. WO 93/04580, WO 96/08475, WO 96/10016, WO 96/14301 or WO 96/33975).

The effectiveness or range of action of these compounds is, however, particularly not always fully satisfied at low application rates and concentrations posed.

New acylated 4-aminopyridines of the formula (I) were found

in which
R ¹ for one of the radicals -CO-Y ¹ , -CO-OY ² , -CO-SY ³ , -CO-NH ₂ , -CO-NH-Y ⁴ , -CO-NY ⁵ Y ⁶ or -SO ₂ - Y ⁷ stands
in which
Y ¹ to Y ⁷ independently of one another represent alkyl, haloalkyl, optionally substituted cycloalkyl or optionally substituted phenyl,
R ^{2 represents} hydrogen or alkyl,
R ^{3 represents} hydrogen, alkyl, halogen, cyano, aminothiocarbonyl or optionally substituted phenyl,
R ^{4 represents} alkyl, alkenyl, optionally substituted cycloalkyl or in each case optionally substituted phenyl or benzyl,
R ^{5 represents} optionally substituted phenyl, for example mono- to tetrasubstituted, identical or differently substituted phenyl, the substituents being halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, nitro, cyano, amino thiocarbonyl, alkylthio, alkylsulfinyl and alkylsulfonyl,
X represents alkyl, halogen, alkoxy or haloalkyl and
n represents 0, 1, 2 or 3,
including the pyridine N-oxides and salts protonated on pyridine nitrogen.

It has also been found that the compounds of the formula (I) can be obtained if

• a) compounds of the formula (II)
  in which
  R ¹ , R ² , R ³ , R ⁵ , X and n have the meaning given above,
  with compounds of the formula (III)
  R ⁴ -O-CO-G (III)
  in which
  R ^{4 has} the meaning given above and
  G represents a leaving group, e.g. B. for halogen (especially chlorine or bromine) or imidazolyl;
  or
• b) compounds of the formula (IV)
  in which
  R ¹ , R ² , R ³ and R ^{4 have} the meaning given above,
  with compounds of formula (V)
  in which
  G, R ⁵ , X and n have the meaning given above,
  each in the presence of a base and optionally in the presence of a diluent;
  or
• c) compounds of the formula (VI)
  in which
  R ² , R ³ , R ⁴ , R ⁵ , X and n have the meaning given above,
  with compounds of formula (VII)
  R ¹ -G (VII)
  in which
  R ¹ and G have the meaning given above,

in the presence of a base and optionally in the presence of a diluent implements.

Finally, it was found that the new compounds of formula (I) are strong have characterized biological properties and especially as fungicides and Control of animal pests, especially insects, arachnids and nematodes, which are used in agriculture, in the forest, in supplies and materials protection as well as in the hygiene sector.

Surprisingly, the acylated 4-aminopyridines according to the invention show one considerably better effectiveness against animal pests than 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 preferably represents one of the radicals -CO-Y ¹ , -CO-OY ² , -CO-SY ³ , -CO-NH ₂ , -CO-NH-Y ⁴ , -CO-NY ⁵ Y ⁶ or -SO ₂ -Y ⁷ ,
in which
Y ¹ to Y ⁷ are each independently preferably C ₁ -C ₄ alkyl, C ₁ -C ₄ - halogenoalkyl having 1 to 5 identical or different halogen atoms, optionally monosubstituted to trisubstituted by identical or different C ₁ -C ₄ alkyl or halogen substituted C ₅ -C ₆ cycloalkyl; or represent phenyl which is optionally monosubstituted to trisubstituted identically or differently, the substituents being halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl having 1 to 5 identical or different halogen atoms, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ haloalkoxy with 1 to 5 identical or different halogen atoms, nitro, cyano, aminothiocarbonyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl and C ₁ -C ₄ alkylsulfonyl in question come.
R ² preferably represents hydrogen or C ₁ -C ₄ alkyl.
R ³ preferably represents hydrogen, C ₁ -C ₄ alkyl, chlorine, bromine, cyano, amino thiocarbonyl or phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, the substituents being halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl with 1 to 5 identical or different halogen atoms, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy with 1 to 5 identical or different halogen atoms, nitro, cyano, aminothiocarbonyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl and C ₁ -C ₄ alkylsulfonyl come into question.
R ⁴ preferably stands for C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, for C ₅ -C ₆ cycloalkyl or C ₁ -C ₄ alkyl or halogen, which is optionally monosubstituted to triple, identical or different, substituted by C ₁ -C ₄ alkyl or halogen for in each case monosubstituted to trisubstituted, identically or differently, phenyl or benzyl, where as substituents in each case halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl having 1 to 5 identical or different halogen atoms, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkoxy with 1 to 5 identical or different halogen atoms, nitro, cyano, aminothiocarbonyl, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfinyl and C ₁ -C ₄ -alkyl sulfonyl come into question.
R ⁵ preferably represents phenyl which is monosubstituted to tetrasubstituted by identical or different substituents, fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkyl and C ₁ being the substituents -C ₄ haloalkoxy, each having 1 to 5 identical or different halogen atoms, nitro, cyano, aminothio carbonyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl and C ₁ -C ₄ alkylsulfonyl.
X preferably represents C ₁ -C ₄ alkyl, fluorine, chlorine, bromine, C ₁ -C ₄ alkoxy or C ₁ - C ₄ haloalkyl having 1 to 5 identical or different halogen atoms.
n is preferably 0, 1 or 2.

Halogen (atoms) is preferably fluorine (atoms), chlorine (atoms) and bromine (atoms).
R ¹ particularly preferably represents one of the radicals -CO-CH ₃ , -CO-C ₂ H ₅ ,

R ² particularly preferably represents hydrogen or methyl.
R ³ particularly preferably represents hydrogen, methyl, phenyl, chlorine, bromine, cyano or aminothiocarbonyl.
R ⁴ particularly preferably represents methyl, ethyl, i-propyl, allyl, cyclohexyl, phenyl or benzyl.
R ⁵ particularly preferably represents phenyl which is mono- or disubstituted by identical or different substituents, fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkyl and C being the substituents ₁ -C ₄ haloalkoxy, each having 1 to 5 identical or different halogen atoms, nitro, cyano, aminothiocarbonyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl and C ₁ -C ₄ alkylsulfonyl.
R ⁵ very particularly preferably represents phenyl substituted by chlorine, cyano, nitro, amino thiocarbonyl, trifluoromethyl, trifluoromethoxy, methylthio, methylsulfinyl or methylsulfonyl.
n particularly preferably represents 0.

The term "halogen atoms" particularly preferably stands for fluorine, chlorine and Bromine atoms.

The radicals listed above or listed in preferred areas Definitions and explanations apply to the end products and to the initial and Intermediates accordingly. These residual definitions can be thus also be combined as desired between the respective preferred areas.

According to the invention, preference is given to the compounds of the formula (I) in which one Combination of the meanings listed above as preferred (preferred) is present.

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 as particularly preferred above, where R ^{5 can} also assume the meanings mentioned as being very particularly preferred.

In the residue definitions listed above and below are hydrocarbons residues, such as alkyl or alkenyl - also in connection with heteroatoms such as alkoxy or alkylthio - if possible straight or branched.  

In addition to the preparation examples, the following compounds of Called formula (Ia):

Table a

If, according to process (a), for example, N- [2- (1-acetyloxyeth-1-yl) -3-chloropyridin-4-yl] -4- (4-cyanophenoxy) phenylacetic acid amide and chloroformic acid isopropyl ester are used as starting materials, the course of the process according to the invention is represented by the following reaction scheme:

If, for example, [2- (1-acetyloxyeth-1-yl)] - 3-chloro-4-isopropoxycarbonylamino-pyridine and 4- (4-cyanophenoxy) phenylacetic acid chloride are used as starting materials in process (b), the course of the process according to the invention is as follows Procedure represented by the following reaction scheme:

According to process (c), for example, N- [3-chloro-2- (1-hydroxyeth-1-yl) pyridin-4-yl] -N-isopropoxycarbonyl-4- (4-cyanophenoxy) phenylacetic acid amide and acetyl chloride are used as starting materials , the course of the process according to the invention is represented by the following reaction scheme:

The compounds of the formula (II) required as starting materials for carrying out process (a) according to the invention are new and are also the subject of the present application. They can be obtained in a generally known manner according to the following general reaction scheme (cf. also the preparation examples):

In the formulas (IIA), (IIB), (II-1) and (IIC), R ² , R ³ , R ⁵ , X and n represent the abovementioned general, preferred and very particularly preferred meanings.

The compounds of the formula (IIA) are known (cf. WO 96/33975 and WO 93/04580) and / or can be obtained by the methods described there.  

The compounds of the formula (IIB) are generally described (cf. WO 93/04580).

The compounds of formula (IIC) are new and also the subject of present application.

The process for producing the N-oxides of formula (IIB), the rearrangement too Compounds of formula (II-1) and the alkaline cleavage to give compounds of Formula (IIC) are based on known methods of organic chemistry (see e.g. J. Med. Chem. 35, 26, pp. 4859-61 (1992)).

To continue to be used as starting materials in process (a) according to the invention The compounds of the formula (III) are generally known compounds of Organic chemistry and / or available according to generally known methods.

The compounds of the formula (IV) required as starting materials for carrying out process (b) according to the invention are new and are likewise the subject of the present application. They are obtained in a generally known manner according to the following general reaction scheme:

In the formulas (IVA), (IVB), (IVC), (IV-1) and (IVD), R ² , R ³ and R ⁴ stand for the general, preferred and particularly preferred meanings mentioned above.

The compounds of the formulas (IVA) and (IVB) are known (cf. WO 96/33975) and / or can be obtained by the methods described there.  

The compounds of the formulas (IVC) and (IVD) are new and also a subject of the present application.

The process of making the N-oxides of formula (IVC), the rearrangement too Compounds of formula (IV-1) and the alkaline elimination to give compounds of the formula (IVD) are based on known organic methods Chemistry (see e.g. J. Med. Chem. 35, 26, pp. 4859-61 (1992)).

To continue to be used as starting materials in process (b) according to the invention The compounds of the formula (V) are generally known compounds of organic chemistry and / or by generally known methods.

The compounds of the formula (VI) required as starting materials for carrying out process (c) according to the invention are new and are also the subject of the present application. They can be obtained in a generally known manner according to the following general reaction scheme:

In the formulas (VIA), (VIB) and (I-1), R ² , R ³ , R ⁴ , R ⁵ , X and n stand for the abovementioned general, preferred and very particularly preferred meanings.

The compounds of the formula (VIA) are known (cf. WO 96/33975) and / or can be obtained using the methods described there.

The compounds of the formulas (VIB) are new and also the subject of this registration.

The process for producing the N-oxides of formula (VIB), the rearrangement too Compounds of formula (I-1) and the alkaline elimination to give compounds of Formula (VI) are based on known methods of organic chemistry (see e.g. J. Med. Chem. 35, 26, pp. 4859-61 (1992)).

Which continue to be used as starting materials in process (c) according to the invention The compounds of the formula (VII) are generally known compounds of organic chemistry and / or by generally known methods.  

The processes (a), (b) and (c) described above for the preparation of the compounds of formula (I) are carried out in the presence of a diluent. As ver All common solvents can be used as diluents.

Halogenated aliphatic or aroma may preferably be used table hydrocarbons, ethers or nitriles such as. B. cyclohexane, toluene, chlorine benzene, chloroform, dichloromethane, dichloroethane, dioxane, tetrahydrofuran, diethyl ether or acetonitrile.

The processes (a), (b) and (c) described above for the preparation of the compounds of the formula (I) are carried out in the presence of a base (cf. also Chem. Ber. 98, 829 (1965); Liebigs Ann. Chem. 739, 201 (1970) and 636 (1973).

All conventional proton acceptors can be used as bases in processes (a), (b) and (c) be used. Alkali or alkaline earth metal hydroxides are preferably usable, Alkali or alkaline earth hydrides, alkali or alkaline earth carbonates or hydrogen carbo nate or nitrogen bases. Examples include sodium hydroxide and calcium hydroxide, sodium hydride, potassium carbonate, sodium hydrogen carbonate, triethylamine, Dibenzylamine, diisopropylamine, pyridine, quinoline, diazabicyclooctane (DABCO), Diazabicyclonones (DBN) and Diazabicycloundecen (DBU).

The reaction temperatures in the processes (a), (b) and (c) described can be varied over a wide range. Generally one works at Tempera doors between -40 ° C and + 200 ° C, preferably between -10 ° C and 100 ° C.

When performing the above-described methods (a), (b) and (c) position of the compounds of formula (I) is generally used per mole of verbin Cations of formula (II) or (IV) or (VI) 1 to 3 moles, preferably 1 to 2 moles Compound of formula (III) or (V) (or (VII).

The pyridine N-oxides and salts of compounds protonated on pyridine nitrogen of the formula (I) can be obtained in a generally customary and known manner  be, for example, in which the compounds of formula (I) with a Oxidizing agents such as B. m-chloroperbenzoic acid or with organic or inorganic acids such as B. trifluoroacetic acid, hydrobromic acid or chlorine implemented hydrochloric acid.

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

The active ingredients are suitable for good plant tolerance and inexpensive warmth blood toxicity to control animal pests, especially insects, Arachnids and nematodes, which are used in agriculture, in forests, in stock and Material protection and in the hygiene sector. You can preferably can be used as pesticides. They are sensitive to normal and resi constant species and effective against all or individual stages of development. To 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 spec.

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 Orthoptera z. B. 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 z. B. Auricular Forficula.

From the order of the Isoptera z. B. Reticulitermes spp. .

From the order of the Anoplura z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.

From the order of 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 spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum 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 maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia po dana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.  

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 chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

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

From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.

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

The plant parasitic nematodes include z. B. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera  spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

The compounds of the formula (I) according to the invention are particularly noteworthy with a high level of insecticidal and acaricidal activity.

They can be used with particularly good success in combating crop damage Insects, such as against the larvae of the horseradish beetle (Phaedon cochleariae) or the caterpillars of the owl butterfly (Spodoptera exigua).

The active ingredients can be converted into the usual formulations, such as Lö solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble Che powder, granules, suspension emulsion concentrates, impregnated with active ingredient Natural and synthetic substances as well as very fine encapsulation in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid Carriers, if necessary using surface-active agents, that is Emulsifiers and / or dispersants and / or foaming agents.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. 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:
e.g. B. ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth or synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: z. B. broken and fractional natural Liche rocks such as calcite, marble, pumice, sepiolite, dolomite or synthetic granules from inorganic and organic flours or granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-generating agents come into question: 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 or protein hydrolyzates; as dispersants come into question: z. B. lignin sulfite or methyl cellulose.

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

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan or organic dyes such as alizarin, azo and metal phthalocyanine dyes or 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 ingredient fabric, preferably between 0.5 and 90%.

The active ingredient according to the invention can be in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, bactericides, Acaricides, nematicides, fungicides, growth regulators or herbi ziden available. Insecticides include, for example, phosphoric acid esters,  Carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, by Microorganisms manufactured substances u. a.

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

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloroN- (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, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Fuberilafil, Fuberri Furmecyclox,
Guazatine,
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, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozolin,
Zineb, ziram

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Teclofta lam, 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, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157419, CGA 184699, Chlorethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Cythrinoshrinothrin, Cythrinothrin, Chrinothrin, Chrinothrin, Chrinothrin, Chrinothrin, Chrinothrin, Chrinothrin, Clotininhrotin, , 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, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, 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, Pyradlmethrhine, Pyradlmethrhine, Pyradlophhrhine, Pyradlmethrin, Pyradlophhrhine, Pyradlophhrhine, Pyradlophhrhine, Pyradlophhrhine, Pyradlophhrhine, Pyrachlophhrhine, Pyradlmethrin, Pyradlophhrhine, Pyradlophhrhine, Pyradlophhrhine, Pyradlophhrhine, Pyradlenthrin, Pyradlophhrin, Pyradlophhrin, Pyradlhethrin, Pyradlenthrin, Pyradlhethrin, Pyradlenthrin, Pyradlhethrin, Pyradlhethhrin, Pyradlenthrin, Pyradlhethhrine, Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio methon, Thionazine, Thuringiensin, Tralometichoniazon, Triaromenhroniaz, Triaratheniazon, Triaratheniazin
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 also be used in their commercially available form formulations and in the use forms prepared from these formulations in Mix with synergists. Synergists are connections through which the Effect of the active ingredients is increased without the added synergist itself must be active.

The active ingredient content of the 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 ingredient, 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 stands out Active ingredient through an excellent residual effect on wood and clay as well as through good stability to alkali on limed substrates.

The active compounds according to the invention act not only against plant, hygiene and Pests, but also against the veterinary sector animal parasites (ectoparasites) such as tortoise ticks, leather ticks, mite 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 as well Ischnocerina e.g. 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 e.g. 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 e.g. 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., Stemostoma 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: Hamsters, guinea pigs, rats and Infest mice. By fighting these arthropods, death traps 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, halters, Mar 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 Apply 100 to 10,000 times dilution or use it as a chemical bath.

It has also been found that the compounds of the formula (I) according to the invention The technical materials show a high insecticidal effect against insects to destroy.

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 rugus, Lyctus pubescescus, Lyctus pubis linearis, Lyctus linearesces rug Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus
Skin wings like
Sirexjuvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur
Termites like
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwinien sis, 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 cardboard, leather, wood and wood processing products and paints.

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

Among wood and wood processing products, which by the invention Agents or mixtures containing them can be protected is exemplary understand: timber, wooden beams, railway sleepers, bridge parts, jetties, Wooden vehicles, boxes, pallets, containers, telephone poles, wooden panels, Wooden windows and doors, plywood, chipboard, carpentry or wood products, which are generally used in house construction or in carpentry.  

The active ingredients can be used as such, in the form of concentrates or in a conventional manner 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, e.g. B. by mixing the active ingredients with at least one solution or Ver thinning agent, emulsifier, dispersing and / or binding or fixing agent, water Repellants, optionally desiccants and UV stabilizers and optionally color substances and pigments as well as 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 agents or concentrates used depends on the type and type come from 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 solution serves as the solvent and / or diluent medium or solvent mixture and / or an oily or oily low 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 low volatility, water Insoluble, oily and oily solvents become corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferred White spirit, petroleum and / or alkylbenzene used.  

Mineral oils with a boiling range of 170 to 220 ° C are advantageous, test petrol 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 substances with a boiling range of 180 to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 up to 220 ° C and / or locker oil and / or monochloronaphthalene, preferably α-mono chloronaphthalene used.

The organic non-volatile oily or oily solvents with a Evaporation rate above 35 and a flash point above 30 ° C, preferably above half 45 ° C, can be partly due to slightly or medium volatile organic chemical Solvents are replaced, with the proviso that the solvent mixture also an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture in this solvent mixture is soluble or emulsifiable.

According to a preferred embodiment, part of the organic chemical Solvent or solvent mixture through an aliphatic polar orga niche 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 the known water-dilutable and / or in the organic used chemical solvents soluble or dispersible or emulsifiable synthetic resins and / or binding drying oils, in particular binders consisting of or containing an acrylic resin, a vinyl resin, e.g. B. polyvinyl acetate, polyester resin, poly  condensation or polyaddition resin, polyurethane resin, alkyd resin or modifi decorated 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 bitumi can also be used as binders nous substances up to 10 wt .-% can be 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 oil contained 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 fixation medium (mixture) or a plasticizer (mixture) can be replaced. These additions are meant to volatilization of the active ingredients and crystallization or precipitation 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 tributylphos phate, 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 mixed with one or more of the above organic chemical solvents or diluents, emulsifiers and dispersants.

A particularly effective wood protection is achieved through industrial impregnation processes, e.g. 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 are particularly preferred mixing partners. Phoxim, Silafluofin, Alphamethrin, Cyfluthrin, Cypermethrin, Deltamethrin, Per methrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron, as well Fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebucon azoles, cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodine-2- propynyl butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazo called lin-3-one.

The active compounds according to the invention also have a strong microbicidal action and can be used to combat unwanted microorganisms be set. The active ingredients are for use as pesticides, esp particularly suitable as fungicides.

Fungicides in crop protection are used to combat plasmo diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basi diomycetes, Deuteromycetes.  

Bactericidal agents are used in plant protection to combat Pseudomonada ceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae used.

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;
Altemaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the control of plants Concentrations necessary for diseases allow treatment above ground Parts of plants, of seedlings, and of the soil.

In addition, they show a broad in vitro activity against phytopathogenic Mushrooms.

When used as fungicides, the active compounds according to the invention can be used as such in Form their customary formulations or the application prepared from them shapes, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble Powders, dusts and granules can be used. The application happens in usual way, e.g. B. by pouring, spraying, spraying, scattering, foaming men, brushing, etc. It is also possible to use the active ingredients according to the ultra-low Apply volume process or the drug preparation or the drug to inject yourself into the ground. It can also be the seed of the plants be treated.

In the treatment of parts of plants, the drug concentrations in the Application forms can be varied in a larger area: They are generally mean between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

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

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

The manufacture and use of the active compounds according to the invention start out the following examples.

Manufacturing examples example 1

(Method a)

To 0.41 g (0.91 mmol) of N- [2- (1-acetyloxyeth-1-yl) -3-chloropyridin-4-yl] -4- (4-cyano phenoxy) phenylacetic acid amide (II-1) in 5 ml of absolute tetrahydrofuran become 0.04 g (1.10 mmol) sodium hydride (60%) added and 1 hour at room temperature temperature stirred. Then 1.82 ml (1.82 mmol) of a 1-molar are at 0 ° C. Solution of isopropyl chloroformate in toluene added dropwise and overnight Room temperature stirred.

For working up, the reaction solution is distributed between ice water and vinegar ester, dries the organic phase and constricts by distilling off the solvent on. After chromatographic purification on silica gel (chloroform / acetone: 95/5) 0.22 g (20% of theory) of N- [2- (1-acetyloxyeth-1-yl) -3-chloropyridine-4- yl] -N-isopropoxycarbonyl-4- (4-cyanophenoxy) phenylacetic acid amide with a logP (pH2) = 4.03.

¹ H-NMR (CDCl ₃ ): 1.10 (d, 6H), 1.30 (d, 3H), 2.05 (s, 3H), 4.35 (s, 2H), 4.95 (m, 1H), 6.15 (m, 1H) , 6.95 (m, 4H), 7.00 (d, 1H), 7.25 (d; 2H), 7.50 (d, 2H), 8.50 (d, 1H) ppm.

[logP = The logP values were determined in accordance with the EEC Directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0.1% aqueous phosphoric acid]  

Manufacture of the starting product

5.0 g (12.3 mmol) of the N-oxide of N- (3-chloro-2-ethyl-pyridin-4-yl) -4- (4-cyano phenoxy) phenylacetic acid amide (IIB-1) are three in 40 ml of acetic anhydride Stirred at 100 ° C for hours. For working up, the mixture is concentrated and the crude product purified chromatographically on silica gel (chloroform / acetone: 95/5).

1.11 g (20% of theory) of N- [2- (1-acetyloxyeth-1-yl) -3-chloropyridine-4- are obtained. yl] -4- (4-cyanophenoxy) phenylacetic acid amide with a logP (pH2) = 2.99.

To 9.79 g (25 mmol) of N- (3-chloro-2-ethyl-pyridin-4-yl) -4- (4-cyanophenoxy) phenyl Acetic acid amide (cf. WO 96/33975) in 250 ml dichloromethane are added in portions 12.32 g (50 mmol) m-chloroperbenzoic acid (70-75%) added and over Stirred at room temperature overnight. The reaction mixture is extracted twice with dilute sodium hydrogen sulfite solution and additionally with 1 normal sodium lye, dries the organic phase and constricts by distilling off the solution by means of a.  

9.33 g (92% of theory) of the N-oxide of N- (3-chloro-2-ethyl-pyridine-4- yl) -4- (4-cyanophenoxy) phenylacetic acid amide with a logP (pH2) = 2.26.

Examples of use

In the following application examples, the compound of the formula (A) known from WO 96/33975 was

used as a reference substance.  

Example A Phaedon larval 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, 1 Ge is mixed most of the 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.

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

In this test, with an exemplary active ingredient concentration of 0.0008% the compound according to preparation example 1 a kill of 100%, while the known compound (A) had no effect after 6 days.  

Example B Spodoptera exigua 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, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

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

In this test, with an exemplary active ingredient concentration of 0.0008% the compound according to preparation example 1 a kill of 100%, while the known compound (A) caused only 50% killing, each after 6 days.

Claims (15)

1. Compounds of formula (I)
in which
R ¹ for one of the radicals -CO-Y ¹ , -CO-OY ² , -CO-SY ³ , -CO-NH ₂ , -CO-NH-Y ⁴ , -CO-NY ⁵ Y ⁶ or -SO ₂ - Y ⁷ stands
in which
Y ¹ to Y ⁷ independently of one another represent alkyl, haloalkyl, optionally substituted cycloalkyl or optionally substituted phenyl,
R ^{2 represents} hydrogen or alkyl,
R ^{3 represents} hydrogen, alkyl, halogen, cyano, aminothiocarbonyl or optionally substituted phenyl,
R ^{4 represents} alkyl, alkenyl, optionally substituted cycloalkyl or in each case optionally substituted phenyl or benzyl,
R ^{5 represents} optionally substituted phenyl, for example mono- to tetrasubstituted, identical or differently substituted phenyl, where halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, nitro, cyano, aminothiocarbonyl, alkylthio, alkylsulfinyl and alkyl sulfonyl are suitable as substituents,
X represents alkyl, halogen, alkoxy or haloalkyl and
n represents 0, 1, 2 or 3,
including the pyridine N-oxides and salts protonated on pyridine nitrogen. 2. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

• a) compounds of the formula (II)
  in which
  R ¹ , R ² , R ³ , R ⁵ , X and n have the meaning given in claim 1,
  with compounds of the formula (III)
  R ⁴ -O-CO-G (III)
  in which
  R ^{4 has} the meaning given in claim 1 and
  G represents a leaving group,
  or
• b) compounds of the formula (IV)
  in which
  R ¹ , R ² , R ³ and R ^{4 have} the meaning given above,
  with compounds of formula (V)
  in which
  G, R ⁵ , X and n have the meaning given above,
  in each case in the presence of a base and optionally in the presence of a diluent;
  or
• c) compounds of the formula (VI)
  in which
  R ² , R ³ , R ⁴ , R ⁵ , X and n have the meaning given above,
  with compounds of formula (VII)
  R ¹ -G (VII)
  in which
  R ¹ and G have the meaning given above,

in the presence of a base and optionally in the presence of a ver implement fertilizer. 3. Compounds of the formula (IIC)
in which
X, n, R ² , R ³ and R ^{5 have} the meaning given in claim 1. 4. Compounds of formula (II)
in which
X, n, R ¹ , R ² , R ³ and R ^{5 have} the meaning given in claim 1. 5. Compounds of the formula (IVC)
in which
R ² , R ³ and R ^{4 have} the meaning given in claim 1. 6. Compounds of the formula (IVD)
in which
R ² , R ³ and R ^{4 have} the meaning given in claim 1. 7. Compounds of formula (IV)
in which
R ¹ , R ² , R ³ and R ^{4 have} the meaning given in claim 1. 8. Compounds of the formula (VIB)
in which
X, n, R ² , R ³ , R ⁴ and R ^{5 have} the meaning given in claim 1. 9. Compounds of the formula (VI)
in which
R ² , R ³ , R ⁴ , R ⁵ , X and n have the meaning given in claim 1. 10. Pesticides and fungicides, labeled by containing at least one compound of the formula (I) according to Claim 1. 11. Use of compounds of formula (I) according to claim 1 for Control of pests and fungi.   12. Process for combating pests and fungi, characterized net that compounds of formula (I) according to claim 1 on pests or fungi and / or their habitat. 13. Process for the preparation of pesticides and fungicides, characterized in that compounds of formula (I) according to An saying 1 mixed with extenders and / or surfactants. 14. Use of compounds of the formula (I) according to Claim 1 for the preparation provision of pesticides and fungicides.