WO1997002237A1 - Fluorobutenic acid oxime esters - Google Patents

Abstract

The invention pertains to fluorobutenic acid oxime esters of formula (I) CF2=CX-CH2-CO-ON=CR1R2 in which: X stands for hydrogen or halogen; R?1 and R2¿ independently of one another stand for hydrogen or (in each case optionally substituted) amino, alkyl, alkenyl, cycloalkyl, alkoxy, alkylthio, aminocarbonyl, alkylcarbonyl, alkyoxycarbonyl, aryl, aralkyl or hetaryl; or alternatively, R?1 and R2¿ together with the carbon atom to which they are bound form a carbocyclic or heterocyclic ring, in either case optionally substituted. The invention also pertains to a process for manufacturing these compounds and the use of the compounds to combat animal pests.

Description

Fluorobutenic acid oxime ester

The present invention relates to new fluorobutenic acid oxime esters, processes for their preparation and their use for controlling animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forests, in the protection of stored products and materials and on hygiene sector occur.

It has already been known that certain fuoralkenyl compounds are effective as insecticides, acaricides and nematicides (see e.g. WO 92/15 555, US-4,952,590, US-4,950,666, US-3,914,251). However, the effectiveness and range of action of these compounds is not always completely satisfactory, especially at low application rates and concentrations.

We have now found new fluorobutenic acid oxime esters of the formula (I)

CF ₂ = CX-CH ₂ -CO-ON = CR ¹ R ² (I)

in which

X represents hydrogen or halogen,

1 7

R and R independently of one another represent hydrogen or optionally substituted amino, alkyl, alkenyl, cycloalkyl, alkoxy, alkylthio, aminocarbonyl, alkylcarbonyl, alkoxycarbonyl, aryl, aralkyl or hetaryl or

R ¹ and R ² together with the carbon atom to which they are attached form an optionally substituted carbocyclic or heterocyclic ring.

The compounds of formula (I) can, depending on the type of

There are substituents as geometric and / or optical isomers or isomer mixtures of different compositions. The invention relates to both the pure isomers and the isomer mixtures. It has furthermore been found that the compounds of the formula (I) are obtained if oximes of the formula (II)

HO-N = CR ^! R ² (II)

in which

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

with an acid chloride of the formula (III)

CF ₂ = CX-CH ₂ -CO-Cl (III)

in which

X has the meaning given above,

optionally in the presence of a diluent and optionally in

In the presence of a base.

Finally, it was found that the new fluorobutenic acid oxime esters of the formula (I) have highly pronounced biological properties and above all to combat animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forests, in the protection of stored products and materials as well as in the hygiene sector are suitable.

Formula (I) generally defines the fluorobutenic acid oxime esters according to the invention.

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

X preferably represents hydrogen or fluorine.

C₁-C₈-Alkylthio, C_r C₈-Halogenalkylthio, C₁-C₆-Alkylthio-C₁-C₆-alkylthio, gegebenenfalls durch C,-C₁₀-Alkyl oder Phenyl (welches gegebenenfalls durch Halogen, C_rC₆-Alkyl, C_rC₆-Halogenalkyl, C_rC₆-Alkoxy oder C_rC₆-Halo- genalkoxy substituiert ist) substituiertes Aminocarbonyl, jeweils gege¬ benenfalls durch Halogen substituiertes C_]-C₈-Alkylcarbonyl oder C,-C₈- Alkoxycarbonyl, jeweils gegebenenfalls durch Halogen, Nitro, Amino,R ¹ and R ² independently of one another preferably represent hydrogen, amino, C-- C ₁₂ alkyl C _r C ₁₂ haloalkyl _; C _r C ₈ alkoxy-C _r C ₈ -alkyl, C, -C ₈ -alkyl-thio-C _r C ₈ -alkyl, optionally substituted by halogen or C _r C ₆ -alkyl ated phenylsulfonyl-C, -C ₄ alkyl, optionally substituted by phenyl, pyridyl, thienyl or pyrrolyl, C ₂ -C ₈ alkenyl, optionally substituted by halogen or C _j -C ₆ alkyl, C ₃ -C ₈ cycloalkyl, C , -C ₈ alkoxy,

C ₁ -C ₈ alkylthio, C _r C ₈ haloalkylthio, C ₁ -C ₆ alkylthio-C ₁ -C ₆ alkylthio, optionally by C, -C ₁₀ alkyl or phenyl (which is optionally substituted by halogen, C _r C ₆ alkyl, C _r C ₆ haloalkyl, C _r C ₆ alkoxy or C _r C ₆ haloalkoxy is substituted) substituted aminocarbonyl, each optionally substituted by halogen C _] -C ₈ alkylcarbonyl or C, -C ₈ - alkoxycarbonyl, in each case optionally by halogen, nitro, amino,

Cyano, SCN, C _r C ₈ alkyl, C _r C ₈ haloalkyl, C _r C ₆ alkoxy, C _r C ₆ - haloalkoxy, C _j -C ₈ alkylthio, C _r C ₆ haloalkylthio or C _r C ₆ -alkoxycarbonyl-substituted phenyl or phenyl-C, -C ₄ -alkyl or for 5- or 6-membered hetaryl optionally substituted by halogen or C, -C ₆ -alkyl having one to three heteroatoms from the nitrogen series,

Oxygen or sulfur,

or

R ¹ and R ² together with the carbon atom to which they are attached form a 4- to 10-membered ring which may contain oxygen, sulfur or nitrogen (which may be substituted by C _] -C ₈ alkyl, phenyl or

Benzyl is substituted), or the rest of the formula

X particularly preferably represents hydrogen or fluorine.

R ¹ and R ² independently of one another particularly preferably represent hydrogen,

Amino, C _r C ₈ alkyl, C _r C ₆ haloalkyl, C _r C ₆ alkoxy-C _r C ₆ alkyl, C _r C ₆ alkylthio-C _j -C ₆ alkyl, optionally by fluorine, chlorine or C, -C ₄ -

Alkyl substituted phenylsulfonyl-C _r C ₂ -alkyl, optionally by Phe- nyl, pyridyl, thienyl or pyrrolyl substituted C ₂ -C ₆ alkenyl, optionally substituted by halogen or C _] -C ₄ alkyl substituted C ₃ -C ₆ cycloalkyl, C, -C ₆ alkoxy, C ^ C ^ Halogenalkoxy, C _] -C ₄ -alkoxy-C ₁ -C ₄ -alkoxy, -C-C ₆ -alkylthio, C, -C ₄ -haloalkylthio, C _r C ₄ -alkylthio-C _r C ₄ -alkylthio, if appropriate by C, -C ₈ alkyl or phenyl (which may be by

Fluorine, chlorine or C _j -C ₄ alkyl is substituted) substituted amino carbonyl, in each case optionally substituted by fluorine or chlorine, C-- C ₆ alkylcarbonyl or C _j -Cg alkoxy carbonyl, in each case optionally by fluorine, chlorine, C , -C ₆ - alkyl, C _r C ₄ haloalkyl, C _r C ₆ alkoxy or C _r C ₄ - haloalkoxy substituted phenyl or phenyl-C _j -C ₂ alkyl or for each optionally by fluorine, chlorine or C ₁ -C ₄ - alkyl substituted pyridyl, pyrimidyl, furyl or thienyl,

or

R ¹ and R ² form, together with the carbon atom to which they are attached form a 4- to 8-membered ring which optionally contains oxygen or Stick¬ material (which is optionally substituted by C _j -C ₈ alkyl) contains.

X very particularly preferably represents fluorine.

gegebenenfalls durch Methyl oder Ethyl substituiertes Phenylsulfonylmethyl, gegebenenfalls durch Phenyl oderR ¹ and R ² independently of one another very particularly preferably represent hydrogen, amino,

phenylsulfonylmethyl optionally substituted by methyl or ethyl, optionally by phenyl or

Thienyl substituted C ₂ -C ₄ alkenyl, cyclopentyl, cyclohexyl, C _r C ₄ alkoxy-C, -C ₄ alkoxy, C _r C ₄ alkyl thio-C, -C ₄ alkylthio, optionally by fluorine or chlorine substituted C _j -C ^ alkylcarbonyl, optionally substituted by fluorine, chlorine or C _r C ₄ - alkyl substituted phenyl, or represents in each case optionally substituted by fluorine, chlorine or C _r C ₄ alkyl substituted pyridyl,

Furyl or thienyl,

or

R ¹ and R ² together with the carbon atom to which they are attached form a 4- to 8-membered carbocycle. The general definitions or explanations or explanations given above, or in preferred areas, apply correspondingly to the end products and to the starting and intermediate products. These residual definitions can be combined with one another as desired, i.e. also between the respective preferred areas.

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

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

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

In the radical definitions listed above and below, hydrocarbon radicals, such as alkyl or alkenyl, are also in connection with heteroatoms, such as

Alkoxy or alkylthio - as far as possible, straight-chain or branched.

If one uses e.g. in the preparation of compounds of formula (I) 4- chloroacetophenone oxime and 3,4,4-trifluorobut-3-ene acid chloride as starting materials, the course of the reaction can be represented by the following reaction scheme:

The process described above for the preparation of compounds of the formula (I) is characterized in that oximes of the formula (II) with the acid chloride of the formula (III) optionally in the presence of a diluent and optionally in the presence of a base.

All customary solvents can be used as diluents.

Halogenated aliphatic or aromatic hydrocarbons, such as cyclohexane, toluene, xylene, dichloromethane, may preferably be used.

Chloroform, dichloroethane or chlorobenzene, nitriles such as acetonitrile, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran or dioxane, amides such as dimethyl formamide or carboxylic acid esters such as ethyl acetate.

It is also possible to work in a two-phase system consisting of an organic solvent and water. Here, for example, the mixtures water / dichloromethane or water / toluene come into question.

In principle, all organic or inorganic bases suitable for such acylations can be used as the base. Amines, in particular tertiary amines such as triethylamine, pyridine, diazabicycloundecene (DBU), diazabicyclonones (DBN) or diazabicyclooctane (DABCO), are also preferably used

Alkali or alkaline earth metal carbonates or hydrogen carbonates such as potassium carbonate, calcium carbonate or sodium hydrogen carbonate, alkali or alkaline earth metal hydroxides such as sodium hydroxide or calcium hydroxide or alkaline earth metal oxides such as calcium oxide.

The reaction temperatures can be varied within a wide range in the process according to the invention. In general, temperatures between -10 ° C and 160 ° C, preferably between 0 ° C and 100 ° C.

In general, the starting materials of the formulas (II) and (III) are used in a molar ratio between 2: 1 and 1: 2.

The reaction is generally carried out at normal pressure.

For example, one can proceed in such a way that the compound of formula (II) is placed in a diluent, the base is added, then the compound of formula (III), optionally dissolved preferably in the same diluent, is added dropwise and the mixture obtained is stirred until the reaction has ended. It is then worked up using customary methods.

The starting materials of the formula (II) used in the process according to the invention are known and / or can be prepared in a simple manner by known processes.

The compounds of the formula (II) are obtained, for example, if carbonyl compounds of the formula (IV)

O = CR * R ² (IV)

in which

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

reacted with hydroxylamine hydrochloride.

The acid chlorides of formula (III) are known (see e.g. US-5 389 680 and EP-432 861).

With good plant tolerance and favorable warm-blood toxicity, the active substances are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forests, in

Storage and material protection as well as in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species and against all or individual stages of development. The pests mentioned above include:

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

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

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

From the order of the Symphyla, for example, Scutigerella immaculata. From the order of the Thysanura, for example Lepisma saccharina.

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

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

Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera e.g. Forficula auricularia.

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

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

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

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

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

From the order of the Homoptera 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, Lithocolleüs blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella spp 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 pseudos Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

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

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

From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp.,

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

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

From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.

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

Plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp ..

The compounds of the formula (I) according to the invention are notable in particular for their outstanding nematicidal activity. For example, they show strong effects against Meloidogyne incognita. They have a systemic effect and can also be used over the leaf.

In addition, they have good leaf insecticidal and acaricidal activity.

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

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foaming 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

Alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl formamide and dimethyl sulfoxide, and water.

Possible solid carriers are: for example ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and Synthetic rock flour, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as Sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and 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% by weight

Active ingredient, preferably between 0.5 and 90%.

The active compound according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.

The following are particularly favorable mixed partners: Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl ^' - trifluoromethoxy ^ '- trifluoro-methyl-l ^ -thiazole-S-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-cy anophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), AI dimoφh, 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, drazoxosolidone, edoloxazidololidolol, epidonolol, epidonolol, epidonolol, epidonol, epidonol, epidonol, epidonol

Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fen¬ propimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Flu-dioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolafosol, Fol- Fthalides, fuberidazole, furalaxyl, furmecyclox, guazatine,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodion, 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, Oxadarbox, Oxadoxcarbox

Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propi conazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilone, quroquilone, quro

Sulfur and sulfur preparations, Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triademenol, triazoxide, trichlamid, tricyclazole, tridemorph, triflorinozoline, triflorizolinol, valid ,

Zineb, ziram.

Bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy¬ cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha¬ methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracbacy, thrifuthrin, bifenulhrin, bensultapin BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorofluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocyentoshrinhrin, Cloferthrin, Cloferthrin, Cyan Cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinone, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu- benzuron, Dimethoat, Di methyvinvin, 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, Flufenproxatophon, Fufionphonophone, Fufionfox, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufone HCH, heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathione, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, NI 25, Nitenpyram, Omethoat, Oxofonon, Oxamyl, Oxamyl, Oxydos

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

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

RH 5992,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,

Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos,

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

Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

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

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

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

The application takes place in a customary manner adapted to the application forms. When used against hygiene and storage pests, the active ingredient is characterized by an excellent residual effect on wood and clay as well as a good stability to alkali on limed substrates.

The active compounds according to the invention act not only against plant, hygiene and stored pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas. These parasites include:

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

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

From the order Diptera and the subordinates Nematocerina as well

Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota ., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp ..

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

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

From the order of the Blattarida, for example Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp .. From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata e.g. Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneu- monyssus spp., Sternostoma spp., Varroa spp ..

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

For example, they show excellent effectiveness against Boophilus microplus and Lucilia cuprina.

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

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

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

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

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

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

The preparation of the compounds of the formula (I) according to the invention will be explained using the following examples:

Manufacturing examples

example 1

To dissolve 4.2 g (25 mmol) of 4-chloroacetophenone oxime in 60 ml of dichloromethane and 2.5 g (25 mmol) of triethylamine are added dropwise at 20 ° C. with stirring

4.0 g (25 mmol) of 3,4,4-trifluorobut-3-ene acid chloride, dissolved in 20 ml of methylene chloride and allowed to stir overnight. The reaction mixture is then washed with dilute hydrochloric acid and water, the organic phase is separated off, concentrated in vacuo and the residue is chromatographed on silica gel in the chloroform system. 3.4 g of 3,4,4-trifluorobut-3-enoic acid (4-chloroacetophenone oxime) ester are obtained as a colorless oil in a yield of 54.9% of theory. Th ..

log p (pH 2) * = 3.52

* log p = decimal logarithm of the n-octanol / water distribution coefficient, determined by HPLC analysis on reversed phase with H ₂ O / CH ₃ CN.

The following compounds of the formula (I) are obtained analogously or according to the general information on the preparation

CF ₂ = CX-CH ₂ -CO-ON = CR ¹ R ² (D

⁹

^

Anwendungsbeispiele ^O

Examples of use

Example A

Limit concentration test / nematodes

Test nematode: Meloidogyne incognita solvent: 4 parts by weight 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, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The active ingredient preparation is mixed intimately with soil that is heavily contaminated with the test nematodes. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (= mg / 1). The treated soil is filled into pots, lettuce is sown and the pots are kept at a greenhouse temperature of 25 ° C.

After four weeks, the lettuce roots are examined for nematode infestation (root galls) and the effectiveness of the active ingredient is determined in%. The degree of efficiency is 100% if the infestation is completely avoided, it is 0% if the infestation is exactly as high as that of the control plants in untreated but contaminated soil in the same way.

In this test, for example, the compounds according to Preparation Examples 4, 6, 8 and 10 had an efficiency of 100% at an exemplary active ingredient concentration of 20 ppm. Example B

Test with fly larvae / development-inhibiting effect

Test animals: All larval stages of Lucilia cuprina (OP-resistant)

[Dolls and adults (without contact with the active ingredient)] Solvent: 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether To produce a suitable formulation, three parts by weight of active ingredient are mixed with seven parts of the solvent / emulsifier mixture mentioned above, and the emulsion concentrate thus obtained is diluted with water to the desired concentration.

30 to 50 larvae per concentration are placed on horse deflector (1 cm ³ ) located in glass tubes, onto which 500 μl of the dilution to be tested are pipetted. The glass tubes are placed in plastic beakers, the bottom of which is covered with sea sand, and stored in an air-conditioned room (26 ° C ± 1.5 ° C, 70% relative humidity + 10%). The effects are checked after 24 hours and 48 hours (larvicidal action). After the larvae have emigrated (approx. 72 h), the glass tubes are removed and perforated plastic lids are placed on the beakers. After 1 1/2 times the development time (hatching of the control flies), the hatched flies and the dolls / doll covers are counted.

The criterion for the effect is the occurrence of death in the treated larvae after 48 h (larvicidal effect), or the inhibition of adult hatching from the pupa or the inhibition of pupa formation. The criterion for the in vitro effect of a substance is the inhibition of flea development or a development standstill before the adult stage. 100% larvicidal activity means that all larvae have died after 48 hours. 100% development-inhibiting effect means that no adult flies have hatched.

In this test, for example, the compound according to Preparation Examples 1, 3, 4, 6 and 8 produced an effect of 100% at an exemplary active ingredient concentration of 1000 ppm. Example C

Test with Boophilus microplus resistant / SP-resistant Parkhurst strain

Test animals: adult sucked females

Solvent: dimethyl sulfoxide

20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide; lower concentrations are produced by dilution in the same solvent.

The test is carried out in 5-fold determination. 1 μl of the solutions is injected into the abdomen, the animals are transferred to dishes and stored in an air-conditioned room. The effect is determined by the inhibition of egg laying. 100% means that no tick has laid.

In this test e.g. the compounds according to the preparation examples 1, 3, 4, 6, 8 and 10 with an exemplary active ingredient concentration of 20 μg per animal have an activity of 100%.

Claims

claims 1. Compounds of formula (I) CF ₂ = CX-CH ₂ -CO-ON = CR ¹ R ² (I) in which X represents hydrogen or halogen, . 1 R and R "independently of one another represent hydrogen or each optionally substituted amino, alkyl, alkenyl, cycloalkyl, alkoxy, alkylthio, aminocarbonyl, alkylcarbonyl, alkoxycarbonyl, aryl, aralkyl or hetaryl or R ¹ and R ² together with the carbon atom to which they are attached form an optionally substituted carbocyclic or heterocyclic ring. 2. Compounds of formula (I) according to claim 1, in which X represents hydrogen or fluorine, R ¹ and R ² independently of one another for hydrogen, amino, C _j -C ₁₂ alkyl C _r C ₁₂ haloalkyl, C _j -C ₈ -alkoxy-C _j -C ₈ alkyl, C _r C ₈ alkylthio _Cι-C8 alkyl, optionally substituted by halogen or _{C] -C6} alkyl substi¬ tuiertes phenylsulfonyl-C, -C ₄ alkyl, optionally substituted by phenyl, pyridyl, thienyl or pyrrolyl substituted C ₂ -C ₈ alkenyl optionally substituted by halogen or C _j -C ₈ alkyl-substituted C ₃ - C ₈ cycloalkyl, C _r C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, C _r C ₆ alkoxy- C _r C ₆ alkoxy, C _r C ₈ alkylthio, C _r C ₈ haloalkylthio, C _r C ₆ -Alkylthio-C, -C ₆ -alkylthio, optionally by C _j -C _{] 0} - alkyl or phenyl (which optionally by halogen, C, -C ₆ alkyl, C, - C ₆ haloalkyl, C _j -C ₆ alkoxy or C _r C ₆ haloalkoxy substi- is substituted) substituted aminocarbonyl, each optionally substituted by halogen C ₁ -C ₈ alkylcarbonyl or C _j -C ₈ alkoxycarbonyl, each optionally substituted by halogen, nitro, amino, cyano, SCN, C _r C ₈ alkyl, C _r C ₈ haloalkyl, C _r C ₆ alkoxy, C _r C ₆ haloalkoxy, C _j -C ₈ alkylthio, C _j -C ₆ haloalkylthio or C _j -C ₆ alkoxy carb onyl substituted phenyl or phenyl C, -C ₄ - alkyl, or represents optionally halogen or C _j -C ₆ - alkyl-substituted 5- or 6-membered hetaryl having one to three heterogeneously atoms from the series nitrogen, oxygen or sulfur, or R ¹ and R ² together with the carbon atom to which they are attached form a 4- to 10-membered ring which is optionally substituted by oxygen, sulfur or nitrogen (optionally substituted by C _j -C ₈ alkyl, phenyl or benzyl is) contains, or the Rest of the formula

3. Compounds of formula (I) according to claim 1, in which X represents hydrogen or fluorine, R ¹ and R ² independently of one another are hydrogen, amino, C _j -C ₈ alkyl, C, -C ₆ haloalkyl, C _j -C ₆ alkoxy-C _j -C ₆ alkyl, C _j -C ₆ - Alkylthio-C _j -C ₆ alkyl, optionally substituted by fluorine, chlorine or C, -C ₄ alkyl substituted phenylsulfonyl-C, -C ₂ alkyl, optionally substituted by phenyl, pyridyl, thienyl or pyrrolyl C ₂ -C ₆ -alkenyl, optionally substituted by halogen or C, -C ₄ - alkyl-substituted C ₃ - C ₆ cycloalkyl, C, -C ₆ alkoxy, C _r C ₄ -haloalkoxy, C, -C ₄ alkoxy C, - C ₄ alkoxy, C _j -C ₆ alkylthio, C _j -C ₄ halo kylthio, C, -C ₄ -Al- kylthio-C _j -C ₄ alkylthio, optionally substituted by C _j -C ₈ alkyl or phenyl (which is optionally substituted by fluorine, chlorine or C _j -C ₄ alkyl) aminocarbonyl, each optionally substituted by fluorine or chlorine C. _j -C ₆ alkyl carbonyl or C, -C ₆ alkoxy carbonyl, each optionally by fluorine, chlorine, C _r C ₆ alkyl, C, -C ₄ haloalkyl, C, -C ₆ alkoxy or C _j -C ₄ -haloalkoxy-substituted phenyl or phenyl-C, -C ₂ -alkyl or represent in each case optionally substituted by fluorine, chlorine or C _r C ₄ -alkyl pyridyl, pyrimidyl, furyl or thienyl, or R ¹ and R ² together with the carbon atom to which they are attached form a 4- to 8-membered ring which optionally contains oxygen or nitrogen - containing (optionally substituted by C _j-C6 stituiert sub¬ alkyl). Compounds of formula (I) according to claim 1, in which X represents fluorine, R ¹ and R ^{2 are} independently hydrogen, amino, C _j -C ₄ alkyl, optionally substituted by methyl or ethyl-substituted Phenylsul- fonylmethyl, optionally substituted by phenyl or thienyl C ₂ -C ₄ alkenyl, cyclopentyl, cyclohexyl, C _j -C ₄ alkoxy-C, - C ₄ alkoxy, C _j -C ₄ alkylthio-C _j -C ₄ alkylthio, optionally substituted by fluorine or chlorine, C _j -C ₄ alkylcarbonyl, optionally substituted by fluorine, chlorine or C _j -C ₄ alkyl stand or sub- stituiertes is optionally substituted by fluorine, chlorine or C _j -C ₄ alkyl are each pyridyl, furyl or thienyl, or R ¹ and R ² together with the carbon atom to which they are attached form a 4- to 8-membered carbocycle. 5. A process for the preparation of compounds of the formula (I) according to claim 1, characterized in that oximes of the formula (II) HO-N = CR ¹ R ² (II) in which R ¹ and R ^{2 have} the meaning given in claim 1, with an acid chloride of the formula (III) CF ₂ = CX-CH ₂ -CO-Cl (III) in which X has the meaning given in claim 1, if appropriate in the presence of a diluent and if appropriate in the presence of a base. 6. pesticides, characterized by a content of at least one compound of the formula (I) according to claim 1. 7. Use of compounds of formula (I) according to claim 1 for combating pests. 8. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat. 9. A process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active agents. 10. Use of compounds of formula (I) according to claim 1 for the manufacture of pesticides.