EP1244633A1

EP1244633A1 - Pyrazolyl benzyl ether derivatives containing a fluoromethoxyimino group and use thereof as pesticides

Info

Publication number: EP1244633A1
Application number: EP00987379A
Authority: EP
Inventors: Ulrich Heinemann; Herbert Gayer; Peter Gerdes; Bernd-Wieland Krüger; Fritz Maurer; Martin Vaupel; Astrid Mauler-Machnik; Ulrike Wachendorff-Neumann; Gerd Hänssler; Karl-Heinz Kuck; Peter Lösel; Christoph Erdelen
Original assignee: Bayer AG; Bayer CropScience AG
Current assignee: Bayer CropScience AG
Priority date: 1999-12-22
Filing date: 2000-12-11
Publication date: 2002-10-02
Also published as: AU2364201A; US6589974B1; JP2003518100A; WO2001046154A1

Abstract

The invention relates to novel pyrazolyl benzyl ethers of formula (I), several methods for production thereof and use thereof for treatment of harmful organisms. The substituents are as defined in claim 1.

Description

PYRAZOLYLBENZYLETHER DERIVATIVES THAT OWN A FLUORMETHOXYIMINO GROUP AND USE THEREOF AS A PEST CONTROL

The invention relates to new pyrazolylbenzyl ethers, several processes for their preparation and their use for controlling harmful organisms.

Certain compounds with a similar substitution pattern and their fungicidal activity have already been disclosed (WO 98/55461, WO 97/07103, WO 96/10556, WO 96/06072, WO 99/33812, DE-A 4424788). However, the action of these previously known compounds is not entirely satisfactory in all areas of application, especially at low application rates and concentrations.

The new pyrazolylbenzyl ethers of the general formula (I) have now been found

in which

A stands for oxygen or -NH-,

R represents in each case optionally substituted alkyl, cycloalkyl or aryl,

L ¹ , L ² , L ³ and L ^{4 are the} same or different and each independently represents hydrogen, halogen, cyano, nitro, each optionally substituted by halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl.

In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkynyl, are also linked to heteroatoms, such as in alkoxy, alkylthio or alkylamino, in each case straight-chain or branched.

Unless otherwise stated, preference is given to hydrocarbon chains having 1 to 6 carbon atoms.

Aryl stands for aromatic, mono- or polycyclic hydrocarbon rings, e.g. Phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, especially phenyl.

Heterocyclyl stands for saturated or unsaturated, as well as aromatic, ring-shaped compounds in which at least one ring member has a hetero atom, i.e. H. is an atom other than carbon. If the ring contains several heteroatoms, these can be the same or different. If the ring contains several oxygen atoms, they are not adjacent. Heteroatoms are preferably oxygen, nitrogen or

Sulfur. If appropriate, the ring-shaped compounds together with other carbocyclic or heterocyclic, fused or bridged rings together form a polycyclic ring system. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic aromatic ring systems. A polycyclic ring system can be linked via the heterocyclic ring or via a fused-on carbocyclic ring.

Cycloalkyl stands for saturated, carbocyclic, ring-shaped compounds which optionally form a polycyclic ring system with other carbocyclic, fused or bridged rings.

Furthermore, it was found that the new pyrazolylbenzyl ethers of the general formula (I) can be obtained if

a) benzyl halides of the formula (II), in which

A, L ¹ , L ² , L ³ and L ^{4 have} the meanings given above and

X represents halogen,

with a substituted pyrazolone of the general formula (III),

(in) in which

R has the meaning given above,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor, or

if

b) Pyrazolylbenzylether of formula (I) with A in its meaning as oxygen with methylamine, optionally in the presence of a diluent. Finally, it was found that the new pyrazolylbenzyl ethers of the general formula (I) have a strong action against harmful organisms, in particular a very strong fungicidal and insecticidal action.

If appropriate, the active compounds according to the invention also have an action against plant pests in certain concentrations and application rates.

The compounds of the invention can optionally be used as mixtures of various possible isomeric forms, in particular stereoisomers, such as. B. E- and Z- are present. Both the E and the Z isomers and any mixtures of these isomers are claimed.

The invention preferably relates to compounds of the formula (I) in which

A stands for oxygen or -NH-,

R represents alkyl having 1 to 8 carbon atoms, in each case optionally cycloalkyl having 3 to 7 carbon atoms which is mono- to disubstituted by halogen, alkyl or hydroxyl; or represents in each case optionally monosubstituted to tetrasubstituted, identical or differently substituted phenyl or naphthyl, the possible substituents preferably being selected from the following list: halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl;

each straight-chain or branched alkyl, hydroxyalkyl, oxoalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulfmyl or alkylsulfonyl each having 1 to 8 carbon atoms; each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms;

each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;

each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms;

straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl, dialkylaminocarbonyloxy,

Alkenylcarbonyl or alkynylcarbonyl, having 1 to 6 carbon atoms in the respective hydrocarbon chains;

Cycloalkyl or cycloalkyloxy each having 3 to 6 carbon atoms;

each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, oxo, methyl, trifluoromethyl or ethyl and in each case doubly linked alkylene having 3 or 4 carbon atoms, oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms;

A ¹

₂ - ^N or a group ^A , wherein

A ^{1 represents} hydrogen, hydroxy or alkyl having 1 to 4 carbon atoms or cycloalkyl having 1 to 6 carbon atoms and A ² for hydroxyl, amino, methylamino, phenyl, benzyl or for alkyl or alkoxy with 1 to 4 carbon atoms optionally substituted by cyano, hydroxy, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl, or for alkenyloxy or alkynyloxy each with 2 is up to 4 carbon atoms,

and in each case optionally in the ring part monosubstituted to trisubstituted by halogen, or or straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms, phenyl, phenoxy, phenyllthio, benzoyl,

Benzoylethenyl, cinnamoyl, heterocyclyl or phenylalkyl, phenylalkyloxy, phenylalkylthio, or heterocyclylalkyl, each having 1 to 3 carbon atoms in the respective alkyl parts,

L ¹ , L ² , L ³ and L ^{4 are the} same or different and are each independently of one another hydrogen, halogen, cyano, nitro, in each case alkyl, alkoxy, alkylthio, alkylsulfmyl or alkylsulfonyl each optionally substituted by 1 to 5 halogen atoms, each having 1 to 6 Carbon atoms.

The invention relates in particular to compounds of the formula (I) in which

A stands for oxygen or -NH-,

R represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl or hexyl, for each in each case optionally one to two times by fluorine, chlorine, methyl,

Ethyl or hydroxy substituted cyclopentyl or cyclohexyl;

or is in each case optionally monosubstituted to tetrasubstituted, identical or differently substituted phenyl or naphthyl, the possible substituents preferably being selected from the list below: Fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl,

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-, 2-, 3-, neo-pentyl, 1-, 2-, 3-, 4- (2nd -Methylbutyl), 1-, 2-, 3-hexyl, 1-, 2-, 3-, 4-, 5- (2-methylpentyl), 1-, 2-, 3- (3-methylpentyl), 2-ethylbutyl, 1-, 3-, 4- (2,2-dimethylbutyl), 1-, 2- (2,3-dimethylbutyl), hydroxymethyl, hydroxyethyl, 3-oxobutyl, methoxymethyl, dimethoxymethyl,

Methoxy, ethoxy, n- or i-propoxy, methoxymethyl, ethoxymethyl,

Methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfmyl, methylsulfonyl or ethylsulfonyl, methylthiomethyl, ethylthiomethyl,

Vinyl, allyl, 2-methylallyl, propen-1-yl, crotonyl, propargyl, vinyloxy, allyloxy, 2-methylallyloxy, propen-1-yloxy, crotonyloxy, propargyloxy;

Trifluoromethyl, trifluoroethyl,

Difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfmyl or trifluoromethylsulfonyl,

Methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethyl a ino,

Acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, dimethylaminocarbonyloxy, diethylaminocarbonyloxy, benzylaminocarbonyl, acryloyl, propioloyl,

Cyclopentyl, cyclohexyl, in each case optionally up to four times, the same or different, substituted by fluorine, chlorine, oxo, methyl or trifluoromethyl, in each case twice linked propanediyl, ethyleneoxy, methylenedioxy, ethylenedioxy

A ¹ 2 "or a grouping ^A , wherein

A ^{1 represents} hydrogen, methyl or hydroxy and

A ^{2 represents} hydroxy, methoxy, ethoxy, amino, methylamino, phenyl, benzyl or hydroxyethyl, and

phenyl, phenoxy, phenylthio, benzoyl, benzoylethenyl, cinnamoyl, benzyl, phenylethyl, phenylpropyl, benzyloxy, in each case optionally in the ring part monosubstituted to triple by halogen and / or straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms.

Benzylthio, 5,6-dihydro-l, 4,2-dioxazin-3-ylmethyl, triazolylmethyl, benzoxazol-2-ylmethyl, l, 3-dioxan-2-yl, benzimidazol-2-yl, dioxol-2- yl, oxadiazolyl and

L ¹ , L ² , L ³ and L ^{4 are the} same or different and are each independently hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s - or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfmyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluorodifluoromethyl, trifluorodifluoromethyl , Trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl.

The invention relates in particular to compounds of the formula (I) in which

A represents oxygen or NH,

R represents phenyl which is in each case monosubstituted or monosubstituted in the same way or differently, the possible substituents preferably being selected from the following list:

Cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-

Butyl, trifluoromethyl,

L ¹ and L ^{3 represent} hydrogen, and

L ² and L ^{4 are} independently hydrogen or methyl.

Another particularly preferred group of compounds

L and L ³ for hydrogen and

L ² and L ^{4 are} independently hydrogen or methyl.

The general or preferred radical definitions given above apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation.

The radical definitions given for these radicals in the respective combinations or preferred combinations of radicals are independently replaced by radical definitions of other preferred ranges independently of the respectively specified combination of the radicals. Formula (II) provides a general definition of the benzyl halides required as starting materials for carrying out process a) according to the invention. In this formula (II), A, L ¹ , L ² , L ³ and L ⁴ preferably or in particular have those meanings which are preferred or particularly preferred in connection with the description of the compounds of the formula (I) according to the invention were preferably given for A, L ¹ , L ² , L ³ and L ⁴ . X represents halogen, preferably chlorine or bromine.

The starting materials of the formula (II) are known and can be prepared by known processes (compare, for example, WO 97/07103, WO 96/10556, WO

96/06072).

Formula (III) provides a general definition of the pyrazolones which are further required as starting materials for carrying out process a) according to the invention. In this formula (III), R preferably or in particular has the meaning which has already been stated as preferred or as particularly preferred for R in connection with the description of the compounds of the formula (I) according to the invention.

The starting materials of the formula (III) are known and / or can be prepared by known methods (compare, for example, Chem. Pharm. Bull. 19, 1389 (1971)).

The pyrazolylbenzyl ethers of the formula (I) with A in their meaning as oxygen, which are required as starting materials for carrying out process b) according to the invention, are compounds according to the invention and can be obtained by process a).

The methylamine which is furthermore required as a starting material for carrying out process b) according to the invention is a generally customary synthetic chemical.

Suitable diluents for carrying out processes a) and b) according to the invention are all inert organic solvents. These include preferably aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as, for example, diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides, such as, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide,

N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as, for example, methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as, for example, methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethyl englycol monomethyl ether,

Diethylene glycol monoethyl ether, their mixtures with water or pure water.

Process a) according to the invention is optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or

Alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate , Potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, and also tertiary amines, such as, for example, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine , N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU). The reaction temperatures can be varied within a substantial range when carrying out process a) according to the invention. In general, temperatures from -20 ° C to 100 ° C, preferably at temperatures from -10 ° C to 80 ° C.

The reaction temperatures can be varied within a substantial range when carrying out process b) according to the invention. In general, temperatures from -20 ° C to 100 ° C, preferably at temperatures from -10 ° C to 50 ° C.

To carry out process a) according to the invention for the preparation of the compounds of the formula (I), 0.5 to 15 mol, preferably 0.8 to 8 mol, of substituted pyrazolone of the formula (III) are generally employed per mole of the benzyl halide of the formula (II) on.

To carry out process b) according to the invention for the preparation of the compounds of the formula (I), 1 to 50 mol, preferably 1 to 10 mol, of methylamine are generally employed per mole of the pyrazolylbenzyl ether of the formula (I) with A in its meaning as oxygen.

Processes a) and b) according to the invention are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.

The reaction is carried out, worked up and isolated according to generally customary methods (see also the preparation examples).

The substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection. Fungicides can be used to protect plants against Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in plant protection to combat Pseudomonadaceae,

Use 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. Lachryrnans; 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);

Coch-iobolus 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 he otrichoides.

The good plant tolerance of the active ingredients in the fight against

Concentrations necessary for plant diseases allow the treatment of above-ground parts of plants, of seedlings, and of the soil.

The active compounds according to the invention can be used with particularly good results in combating cereal diseases, for example against erysiphe-,

Leptosphaeria, or Puccinia species, of diseases in wine, fruit and vegetable cultivation, such as, for example, against Alternaria, Venturia, Sphaerotheca and Plasmopara species, or of rice diseases, such as, for example, against Pyricularia species.

The active substances according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.

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

With good plant tolerance and favorable warm-blood toxicity, the active substances are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:

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

From the order of the Diplopoda e.g. Blaniulus guttulatus.

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

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

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

From the order of the Collembola e.g. Onychiurus armatus.

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

From the order of the Blattaria, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica. From the order of the Dermaptera, for example, Forficula auricularia.

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

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

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

From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus sppe, Phrosiphodumonum., Macrosiphodumon. 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 e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisispppp., Phyllocnist.

Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola pissellellaella, Tineola pissellellaella podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,

Cnaphalocerus spp., Oulema oryzae. From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysoisisamamisysamnaisphamisusnaisphamusisnaamyszaamiszaamysaza sylasylamisusnaamphasylasphis, amphora spp.

Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meliginusus seneus. Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.

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

From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata,

Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp ..

From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp ..

From the class of the Arachnida, for example, Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Omithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyal ., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus 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., Tripusichpp. Spp., Xiphinema spp. ,

They can be used with particularly good success for combating plant-damaging insects, such as, for example, against the larvae of the horseradish beetle (Phaedon cochleariae), the green peach aphid (Myzus persicae), and plant-damaging nematodes, such as Meloidogyne incognita.

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and undesirable wild plants or crop plants (including naturally occurring crop plants). Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights. Under plant parts, all above-ground and underground parts and organs of the

Plants, such as shoots, leaves, flowers and roots, are to be understood, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

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

In the present context, technical materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention, adhesives, glues, paper and cardboard, textiles, leather, wood, paints and

Plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms. In the context of the materials to be protected, parts of production plants, for example cooling water circuits, are also mentioned which can be impaired by the multiplication of microorganisms. In the context of the present invention are considered technical

Materials preferably called adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer fluids, particularly preferably wood.

As microorganisms that break down or change the technical

Bacteria, fungi, yeasts, algae and slime organisms can be mentioned as materials. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

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

Altemaria, such as Altemaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Pechichomonas, such as Escherichiaiaosine, such as Escherichia, as well as like Staphylococcus aureus.

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

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or

Methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous extenders or carriers mean liquids which are at normal temperature and under normal are gaseous in pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide. Solid carrier materials are suitable: for example natural rock powder, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates. As fixed

Carriers for granules are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Possible emulsifiers and / or foaming agents are: e.g. 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 dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.

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

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

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be mixed with known fungicides, bactericides, acaricides, nematicides or insecticides can be used, for example to spread the spectrum of activity or prevent the development of resistance. In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

fungicides:

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

azoxystrobin,

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

Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazon, chlorfenazol, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyofiaminol, cypodirconol

Debacarb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, di ethirimol, dimethomoφh, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianonodol, dithianonodol, dithianonodol, dithianonol, dithianonodol,

Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,

Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,

Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconazol, Flirrprimidol, Flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-alminium, fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,

guazatine,

Hexachlorobenzene, hexaconazole, hymexazole,

Lmazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan,

Isovaledione,

Kasugamycin, Kresoxim-m ethyl, copper preparations such as: copper hydroxide, copper phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfiiroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,

Paclobutrazole, pefiirazoate, penconazole, pencycuron, phosdiphen, pimaricin,

Piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamocarb, propanosine sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

Quinconazole, quintozen (PCNB), Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tri- cyclazol, tridemorph, triflumizole, triforine, Triticonazole, uniconazole,

Validamycin A, vinclozolin, viniconazole,

Zarilamid, Zineb, Ziram as well

Dagger G,

OK 8705,

OK 8801,

α- (l, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1H- 1, 2,4-triazole-1-ethanol, α- (2,4-dichloφhenyl) -ß-fluoro-b-propyl- lH-l, 2,4-triazole-l-ethanol, - (2,4-dichloφhenyl) -ß-methoxy-a-methyl-lH-l, 2,4-triazole-l-ethanol, α- (5- Methyl-l, 3-diox - n-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] -lH-l, 2,4-triazol-1-ethanol,

(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-l, 2,4-triazol-l-yl) -3-octanone, (E) -a- (methoxyimino ) -N-methyl-2-phenoxy-phenylacetamide,

{2-methyl- 1 - [[[[- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid -

1-isopropyl ester l- (2,4-dichloφhenyl) -2- (lH-l, 2,4-triazol-l-yl) -ethanone-O- (phenylmethyl) oxime,

1 - (2-methyl-1-naphthalenyl) - lH-pyrrole-2,5-dione, l- (3,5-dichloro-henyl) -3- (2-propenyl) -2,5-pyrrolidinedione, l - [( diiodomethyl) sulfonyl] -4-methyl-benzene, l - [[2- (2,4-dichlorophenyl) -1, 3-dioxolan-2-yl] methyl] -1 H -imidazole, l - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl ] -lH-l, 2,4-triazole, l- [l- [2 - [(2,4-dichloφhenyl) methoxy] phenyl] ethenyl] -lH-imidazole, l-methyl-5-nonyl- 2- (phenylmethyl) -3-pyrrolidinol, 2 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-l, 3-thiazole-5-carboxanilide,

2,2-dichloro-N- [l- (4-chloφhenyl) ethyl] -l-ethyl-3-methyl-cyclopropanecarboxamide,

2, 6-dichloro-5 - (methylthio) -4-p yrimidiny 1-thi ocyanate,

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

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

2 - [(l-methylethyl) sulphonyl] -5- (trichloromethyl) -l, 3,4-thiadiazole,

2 - [[6-Deoxy-4-O- (4-O-methyl-ß-D-glycopyranosyl) -aD-glucopyranosyl] -amino] -4- methoxy-lH-pyrrolo [2,3-d] pyrimidine- 5-carbonitrile, 2-aminobutane,

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

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

2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) -acetamide,

2-phenylphenol (OPP), 3,4-dichloro-l- [4- (difluoromethoxy) pheny]] - 1H-pyrrole-2,5-dione,

3,5-dichloro-N- [cyano [(l-methyl-2-propynyl) -oxy] -methyl] -benzamide,

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

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

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

8- (l, l-dimethylethyl) -N-ethyl-N-propyl-l, 4-dioxaspiro [4.5] decane-2-methanamine,

8-hydroxyquinoline sulfate,

9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide, bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate, ice 1 - (4-chloro-phenyl) -2- (1 H-1, 2,4-triazol-1-yl) -cycloheptanol, cis-4- [3- [4- (l, l-dimethylpropyl) phenyl-2-methylpropyl] -2,6-dimethyl-moφholin hydrochloride,

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

Potassium hydrogen carbonate, methane tetrathiol sodium salt,

Methyl 1 - (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) - 1 H-imidazole-5-carboxylate,

Methyl-N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,

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

N- (2,3-dichloro-4-hydroxyphenyl) -1-methyl-cyclohexane carboxamide. N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,

N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,

N- (4-cyclohexylphenyl) - 1, 4,5, 6-tetrahydro-2-pyrimidinamine,

N- (4-hexylphenyl) -l, 4,5,6-tetrahydro-2-pyrimidinamine, N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) - acetamide,

N- (6-methoxy) -3-pyridinyl) -cyclopropanecarboxamide,

N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide,

N- [3-chloro-4,5-bis- (2-propynyloxy) -phenyl] -N'-methoxy-methanimidamid,

N-formyl-N-hydroxy-DL-alanine sodium salt, O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate,

O-methyl-S-phenyl-phenylpropylphosphoramidothioate,

S-methyl-1, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] -l-benzopyran-2, 1 '(3Η) -isobenzofuran] -3'-one,

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, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos A, Azinphos M, Azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfiiracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Bioethanominocin, Bomethophenin

Butocarboxime, butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloφyrifos, Chloφyrifos M, Chlovaporthrin, Cis-Resmethrin,

Cispermethrin, clocythrin, cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

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

Docusat-sodium, Dofenapyn,

Eflusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrine

Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazuron, Flubrocythrinate, Flucycloxuron, Flucythrinate, Flufenoxuron, Flutenzine, Fluvalinate, Fonophos, Fosmethilan, Fosthproxate, Fosthproxate, Fosthproxate,

granulosis Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,

Imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,

Kempolyederviren

Lambda cyhalothrin, lufenuron

Malathion, mecarbam, metaldehyde, methamidophos, metharhilic anisopliae,

Metharhilic flavoviride, methidathione, methiocarb, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, monocrotophos, naled, nitenpyram, nithiazine, novaluron

Omethoate, Oxamyl, Oxydemethon M

Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propoxur, Prothiofos, Prothoat, Pyromclhrinos, Pymmethrofinos Pyridaben, pyridathione, pyrimidifen,

pyriproxyfen,

quinalphos,

ribavirin

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

Tau fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, theta-cypermethrin, thiamethoxam, thiapronil, thiatriphamos, thi oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathenes, triazamates, triazophos, triazuron, trichlophenidines, trichlorfon, triflumuron, trimethacarb,

Vamidothion, Vaniliprole, Verticillium lecanii

YI 5302

Zeta-cypermethrin, zolaprofos

(IR-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) - furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate

(3-phenoxyphenyl) methyl 2,2,3,3-tetramethylcyclopropane decarboxylate l - [(2-chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-l, 3,5-triazine -2 (lH) - imine

2- (2-Chloro-6-fluoφhenyl) -4- [4- (l, l-dimethylethyl) phenyl] -4,5-dihydro-oxazole 2- (acetyloxy) -3-dodecyl-1, 4-naphthalenedione

2-chloro-N - [[[4- (l-phenylethoxy) phenyl] amino] carbonyl] -benzamide

2-chloro-N - [[[4- (2,2-dichloro-l, l-difluoroethoxy) -phenyl] -amino] -carbonyl] -benzamide

3-methylphenyl propyl carbamate - [4- (4-ethoxyphenyl) -4-methylpentyl] -l-fluoro-2-phenoxy-benzene-chloro-2- (1, 1-dimethylethyl) -5 - [[2- (2 , 6-dimethyl-4-phenoxyphenoxy) ethyl] thio] - (2H) -pyridazinone 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone

4-chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichloφhenyl) -3 (2H) -pyridazinone

Bacillus thuringiensis strain EG-2348

Benzoic acid [2-benzoyl-1 - (1, 1-dimethylethyl) hydrazide

Butanoic acid 2,2-dimethyl-3- (2,4-dichloro phhenyl) -2-oxo-1-oxaspiro [4.5] dec-3-en-4-yl ester

[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] -cyanamide

Dihydro-2- (nitromethylene) -2H-l, 3-thiazine-3 (4H) carboxaldehyde

Ethyl [2 - [[1,6-dihydro-6-oxo-l- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] carbamate N- (3,4,4-trifluoro-l-oxo-3- butenyl) -glycine

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

1-carboxamide

N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine

N-methyl-N '- (1-methyl-2-propenyl) - 1, 2-hydrazinedicarbothioamide

N-methyl-N'-2-propenyl-1, 2-hydrazine dicarbothioamide

O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

In addition, the compounds of the formula (I) according to the invention also have very good antifungal effects. They have a very broad anti-mycotic spectrum of activity, in particular against dermatophytes and shoots, mold and diphasic fungi, e.g. against Candida species such as Candida albicans or Candida glabrata; Epidermophyton species such as Epideπnophyton floccosum; Aspergillus species such as Aspergillus niger and Aspergillus fumigatus; Trichophyton species such as Trichophyton mentagrophytes; Microsporon species such as Microsporon canis and audouinii. The list of these fungi is in no way a limitation of the detectable mycotic spectrum, but is only of an explanatory nature.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by watering, spraying, atomizing, scattering, dusting, 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 into the soil itself. The seeds of the plants can also be treated.

When using the active compounds according to the invention as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application.

In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. When treating the floor the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

When used as insecticides, the active compounds according to the invention can 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 that increase the effectiveness of the active ingredients 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

Wise.

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.

Preparation Examples:

example 1

5.3 g (0.0275 mol) l- (4-chloro-phenyl) -l, 2-dihydro-3H-pyrazol-3-one, 10 g (0.0275 mol) 2- [2- (bromomethyl) phenyl] -2 - [(fluoromethoxy) imino] methyl acetate (84%) and 1.1 g (0.0275 mol) sodium hydride (60%) are stirred in 40 ml dry dimethylformamide at room temperature for 18 hours. The solvent is then distilled off under reduced pressure. The residue is taken up in 50 ml of ethyl acetate and washed several times with water. The organic phase is dried over sodium sulfate and concentrated under reduced pressure. The residue is chromatographed on silica gel using hexane / acetone (8: 2). 5 g (43.5% of theory) of 2- [2 - ({[1- (4-chloro-phenyl) - 1H-pyrazol-3-yl] oxy} methyl) phenyl] -2 - [(fluoromethoxy) imino are obtained ] methyl acetate.

HPLC: logP = 3.86

Example 2

4 g (0.007 mol) of 2- [2 - ({[l- (4-chloro-phenyl) -lH-pyrazol-3-yl] oxy} methyl) phenyl] -2- [(fluoromethoxy) imino] methyl acetate are dissolved in 30 ml Dissolved methanol and then introduced about 0.7 g (0.02 mol) of methylamine, the solution heating to about 30 ° C. This mixture is stirred at room temperature for 18 hours and then the solvent is distilled off under reduced pressure. The residue is taken up in 50 ml of ethyl acetate and washed several times with water. The organic phase is dried over sodium sulfate and again concentrated under reduced pressure. The residue is chromatographed on silica gel using hexane / acetone (8: 2). 1.8 g (60.5% of theory) of 2- [2 - ({[l- (4-Chlθφhenyl) -lH-pyrazol-3-yl] oxy} methyl) phenyl] -2 - [(fluoromethoxy ) imino] -N-methylacetamide.

HPLC: logP = 3.30

Analogously to Examples 1 and 2, and in accordance with the information in the general process descriptions, the compounds of the formula (I-a) mentioned in Table 1 below are obtained.

Table 1:

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

applications

Example A

Erysiphe test (barley) / protective

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

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

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

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate.

After the spray coating has dried on, the plants are covered with spores from Erysiphe graminis f.sp. hordei pollinated.

The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% to prevent the development of

Favor mildew pustules.

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

In this test, the substance according to the invention listed in Example (2) shows an efficiency of 98% or more at an application rate of 250 g / ha. Example B

Puccinia test (wheat) / protective

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

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

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

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

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

In this test, the substance according to the invention listed in Example (1) shows an efficiency of 98% or more at an application rate of 250 g / ha. Example C

Puccinia test (wheat) / curative

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

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To test for curative effectiveness, young plants are sprayed with a condiment suspension from Puccinia recondita. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours. The plants are then sprayed with the active compound preparation in the stated application rate.

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

In this test, the substance according to the invention listed in Example (2) shows an efficiency of 98% or more at an application rate of 250 g / ha. Example D

Plasmopara test (vine) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacaetamide emulsifier: 1.0 part by weight of alkylaryl polyglycol ether

To test for protective activity, young plants are sprayed with the preparation of active compound in the application rate given. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Plasmopara viticola and then remain in an incubation cabin at about 20 ° C. and 100% relative atmospheric humidity for 1 day. The plants are then placed in a greenhouse at about 21 ° C. and about 90% relative atmospheric humidity for 5 days. The plants are then moistened and placed in an incubation cabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, those shown in Examples (1, 2, 3, 4, 5, 6, 7, 8, 11, 13, 14, 15, 16, 17, 18, 19, 26, 27, 28 and 31) show Substances according to the invention with an application rate of 100 g ha an efficiency of 95% or more. Example E

Sphaerotheca test (cucumber) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide emulsifier: 1.0 part by weight of alkylaryl polyglycol ether

To test for protective efficacy, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are washed with an aqueous spore suspension of

Sphaerotheca fuliginea inoculated. The plants are then placed in the greenhouse at about 23 ° C. and a relative atmospheric humidity of about 70%.

In this test, those shown in Examples (1, 2, 3, 4, 5, 6, 7, 8, 11, 13, 14, 15, 16, 17, 18, 19, 26, 27, 28 and 31) show Substances according to the invention at an application rate of 100 g / ha an efficiency of 93% or more.

Example F

Venturia test (apple) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide emulsifier: 3 parts by weight of alkylaryl polyglycol ether

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

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

Evaluation is carried out 12 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, those shown in Examples (1, 2, 3, 4, 5, 6, 7, 8, 11, 13, 14, 15, 16, 17, 18, 19, 26, 27, 28 and 31) show Substances according to the invention at an application rate of 10 g / ha an efficiency of 98% or more. Example G

Pyricularia test (rice) / protective

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

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To test for protective activity, young rice plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae and then remain at 100% rel. Humidity and 26 ° C. The plants are then in a greenhouse at 80% rel. Humidity and a temperature of 26 ° C.

In this test, the substances according to the invention listed in Examples (1,2) show an efficiency of 60% or more at an application rate of 125 g / ha. Example H

Altemaria test (tomato) / protective

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

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To test for protective activity, young tomato plants are sprayed with the preparation of active compound in the stated application rate. 1 day after the treatment, the plants are inoculated with a spore suspension of Alternaria solani and then stand at 100% rel. Humidity and 20 ° C. Then the plants are at 96% rel. Humidity and a temperature of 20 ° C. Evaluation is carried out 7 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances according to the invention listed in examples (1, 2) show an efficiency of 80% or more at an application rate of 750 g / ha.

Example I

Leptosphaeria nodorum test (wheat) / protective

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

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To test for protective activity, young wheat plants are sprayed with the preparation of active compound in the stated application rate. 1 day after the treatment, the plants are inoculated with an aqueous spore suspension of Leptosphaeria nodorum and then remain at 100% rel. Humidity and 20 ° C. The plants are then in a greenhouse at 80% rel. Humidity and a temperature of 22 ° C.

Evaluation is carried out 12-14 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances according to the invention listed in Examples (1, 2) show an efficiency of 94% or more at an application rate of 750 g / ha. Example J

Phaedon larvae test

Solvent: 30 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired amount with water containing emulsifier

Concentration.

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

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

In this test, the substance according to the invention listed in Example (1) shows a degree of destruction of 100% at an active substance concentration of 1000 ppm.

Example K

Myzus Test

Solvent: 30 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

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

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

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

In this test, the substance according to the invention listed in Example (1) shows a degree of destruction of 95% at an active substance concentration of 1000 ppm.

Claims

claims

Compounds of the general formula (I),

in which

A stands for oxygen or -NH-,

R represents in each case optionally substituted alkyl, cycloalkyl or aryl,

L ¹ , L ² , L ³ and L ^{4 are the} same or different and each independently represents hydrogen, halogen, cyano, nitro, each optionally substituted by halogen substituted alkyl, alkoxy, alkylthio, alkylsulfmyl or alkylsulfonyl.

2. Compounds of formula (I), according to Anspmch 1, characterized in that

A stands for oxygen or -NH-,

R for alkyl with 1 to 8 carbon atoms, for cycloalkyl having 3 to 7 carbon atoms which is optionally mono- to disubstituted by halogen, alkyl or hydroxyl;

or is in each case optionally monosubstituted to tetrasubstituted, identical or differently substituted phenyl or naphthyl, the possible substituents preferably being selected from the list below:

Halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarboxyl;

each straight-chain or branched alkyl, hydroxyalkyl, oxoalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulfmyl or alkylsulfonyl each having 1 to 8 carbon atoms;

each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms;

each straight-chain or branched haloalkyl, haloalkoxy,

Haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;

each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl, dialkyl aminocarbonyloxy, alkenylcarbonyl or alkynylcarbonyl, having 1 to 6 carbon atoms in the respective hydrocarbon chains;

Cycloalkyl or cycloalkyloxy each having 3 to 6 carbon atoms;

each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, oxo, methyl, trifluoromethyl or ethyl and in each case doubly linked alkylene with 3 or 4 carbon atoms, oxyalkylene with 2 or 3 carbon atoms or dioxyalkylene with 1 or 2 carbon atoms ;

A ¹

- N or a group ^A , in which

A ^{1 represents} hydrogen, hydroxy or alkyl having 1 to 4 carbon atoms or cycloalkyl having 1 to 6

Carbon atoms stands and

A ² for hydroxyl, amino, methylamino, phenyl, benzyl or for alkyl or alkoxy each having 1 to 4 carbon atoms which is optionally substituted by cyano, hydroxy, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl, or for alkenyloxy or alkynyloxy each having 2 to 4 Carbon atoms,

and in each case in the ring part, if necessary, through to three times

Halogen, and / or straight-chain or branched alkyl or alkoxy with 1 to 4 carbon atoms substituted phenyl, phenoxy, phenylthio, benzoyl, benzoylethenyl, cinnamoyl, heterocyclyl or phenylalkyl, phenylalkyloxy, phenylalkylthio, or heterocyclylalkyl, each with 1 to 3 carbon atoms in the respective alkyl parts . L ¹ , L ² , L ³ and L ^{4 are} identical or different and, independently of one another, each represent hydrogen, halogen, cyano, nitro, in each case alkyl, alkoxy, alkylthio, alkylsulfmyl or alkylsulfonyl, each of which is optionally substituted by 1 to 5 halogen atoms are up to 6 carbon atoms.

3. Compounds of formula (I), characterized in that

A stands for oxygen or -NH-,

R is methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl or

Hexyl, for cyclopentyl or cyclohexyl which is optionally mono- to disubstituted by fluorine, chlorine, methyl, ethyl or hydroxyl;

Fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl,

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-, 2-, 3-, neo-

Pentyl, 1-, 2-, 3-, 4- (2-methylbutyl), 1-, 2-, 3-hexyl, 1-, 2-, 3-, 4-, 5- (2-methylpentyl), 1 -, 2-, 3- (3-methylpentyl), 2-ethylbutyl, 1-, 3-, 4- (2,2-dimethylbutyl), 1-, 2- (2,3-dimethylbutyl), hydroxymethyl, hy- droxyethyl, 3-oxobutyl, methoxymethyl, dimethoxymethyl,

Methoxy, ethoxy, n- or i-propoxy, methoxymethyl, ethoxymethyl, Methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, methylthiomethyl, ethylthiomethyl,

Trifluoromethyl, trifluoroethyl,

Difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl,

Methylamino, ethylamino, n- or i-propylamino, dimethylamino,

diethylamino,

Cyclopentyl, cyclohexyl,

in each case optionally up to four times, the same or different, substituted by fluorine, chlorine, oxo, methyl or trifluoromethyl, in each case twice linked propanediyl, ethyleneoxy, methylendioxy, ethylenedioxy

A ¹

or a grouping _A ² "^, where A ^{1 represents} hydrogen, methyl or hydroxy and

phenyl, phenoxy, phenylthio, benzoyl, benzoylethenyl, cinnamoyl, benzyl, phenylethyl, phenylpropyl, benzyloxy, benzylthio, 5, in each case optionally in the ring part monosubstituted to triple by halogen, and or straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms, 6-dihydro-l, 4,2-dioxazin-3-ylmethyl, triazolylmethyl, benzoxazol-2-ylmethyl, 1,3-dioxan-2-yl, benzimidazol-2-yl, dioxol-2-yl, oxadiazolyl and

L ¹ , L ² , L ³ and L ^{4 are} identical or different and are each independently of one another hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl,

Ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, di - Fluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfmyl or trifluoromethylsulfonyl are available.

4. Compounds of formula (I), characterized in that

A stands for oxygen or -NH-,

R in each case represents phenyl which is monosubstituted or disubstituted in the same way or differently, the possible substituents preferably being selected from the following list: Cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl

L ¹ and L ^{3 represent} hydrogen, and

L ² and L ^{4 are} independently hydrogen or methyl.

5. A process for the preparation of compounds of formula (I), as defined in Anspmch 1, characterized in that

a) compounds of the formula (II),

in which

A, L ¹ , L ² , L ³ and L ^{4 have} the meanings given above and

X represents halogen,

with compounds of the general formula (III),

in which

R has the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor, or

if

b) compounds of formula (I) with A in its meaning as oxygen with methylamine, optionally in the presence of a diluent.

6. Agents for combating harmful organisms containing extenders and / or carriers and optionally surface-active substances, characterized by a content of at least one compound as defined in claims 1 to 4.

7. A method for controlling harmful organisms, characterized in that compounds as defined in claims 1 to 4 or agents as defined in Claim 6 are allowed to act on harmful organisms and / or their habitat.

8. Use of compounds as defined in claims 1 to 4 or agents as defined in Anspmch 6 for combating harmful organisms.

9. A process for the preparation of agents as defined in Anspmch 6, characterized in that compounds as defined in claims 1 to 4 are used with extenders and / or carriers and / or surface-active agents.