WO1997008132A1 - Fluorobutene acid amides - Google Patents

Abstract

The present invention relates to new fluorobutene acid amides of formula (I), in which R1 is hydrogen or halogen; R2 is hydrogen, alkyl or phenyl optionally substituted by halogen or alkyl; R3 is one of the residues specified under a); b); c), wherein a methylene group is optionally replaced by SO¿2?, or one or two not directly adjacent methylene groups are replaced by oxygen, sulphur or nitrogen (which is optionally substituted by alkyl, phenyl or benzyl); or d) 5 or 6-membered hetarylalkyl optionally substituted by alkyl or by phenyl optionally substituted by halogen, alkyl, alkyl halide, alkoxy or alkoxy halide, and one to three heteroatoms from the series of oxygen, sulphur and nitrogen; or e) is benzthiazolyl or pyridyl in each case optionally substituted by halogen, alkyl or alkyl halide, wherein X, Y, Z, R?4¿, W, n, l and m have the meaning given in the description. It also relates to a method for the preparation thereof, and the use thereof for the control of animal pests.

Description

Fluorobutenic acid amides

The present invention relates to new fluorobutenic acid amides, ner processes for their preparation and their use for controlling animal pests, in particular insects, arachnids and Νematodes, which occur in agriculture, in forests, in the protection of stocks and materials and in the hygiene sector.

From WO 92/15 555 it is known that the compounds Ν-phenyl-3,4,4-trifluorobut-3-enoamide and N- (3-carboxyphenyl) -3,4,4-trifluorobut-3-enoamide have insecticidal, acaricidal and nematicidal properties. Fluorovinylcarboxamide derivatives with insecticidal and acaricidal properties are known from EP-A-0 661 289.

The effectiveness and range of action of these compounds is, however, not always completely satisfactory, especially at low application rates and concentrations.

New fluorobutenamides of the formula (I) have now been found

in which

R ^{1 represents} hydrogen or halogen,

R ^{2 represents} hydrogen, alkyl or phenyl which is optionally substituted by halogen or alkyl,

R ³ for a) stands

woπn

woπn

X represents amino, hydroxy, mercapto, nitro, cyano, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, alkylamino, dialkylamino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl or haloalkenylcarbonylamyl

Y and Z independently of one another represent hydrogen, amino, hydroxy, mercapto, cyano, carboxyl, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylcarbonyl, alkoxycarbonyl, alkylamino, dialkylamino, alkylamino carbonyl or dialkylaminocarbonyl or

worinb) stands,

wherein

X and Y have the meaning given above,

R ^{4 represents} hydrogen or alkyl and

n stands for 0, 1, 2, 3 or 4 or

worinc) stands

wherein

optionally a methylene group is replaced by SO ₂ or one or two not directly adjacent methylene groups in the ring are replaced by oxygen, sulfur or nitrogen (which is optionally substituted by alkyl, phenyl or benzyl),

1 represents 0, 1 or 2,

m represents 0, 1, 2, 3, 4 or 5 and

W represents halogen, alkyl or phenyl which is optionally substituted by halogen, alkyl, haloalkyl, alkoxy or haloalkoxy or

d) 5- or 6-membered hetarylalkyl optionally substituted by halogen, alkyl or by phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy or haloalkoxy is one to three heteroatoms from the series consisting of oxygen, sulfur and nitrogen or

e) pyridyl or benzthiazolyl optionally substituted by halogen, alkyl or haloalkyl.

Depending on the nature of the substituents, the compounds of the formula (I) can be present as geometric and / or optical isomers or isomer mixtures of different compositions. The invention relates to both the pure

Isomers as well as the isomer mixtures.

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

Amines of formula (II)

HNR ² R ³ (II)

in which R ² and R ^{3 have} the meaning given above,

with acid chlorides of the formula (III)

in which

R ^{1 has} the meaning given above,

if appropriate in the presence of a diluent and if appropriate in the presence of a base.

Finally, it was found that the new fluorobutenic acid amides of the formula (I) have highly pronounced biological properties and above all to control animal pests, in particular insects, arachnids and

Nematodes that are used in agriculture, in forests, in supply and material protection and in the hygiene sector are suitable.

Formula (I) provides a general definition of the fluorobutenamides according to the invention.

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

R ¹ preferably represents hydrogen, fluorine, chlorine or bromine.

R preferably represents hydrogen, C ₁ -C ₆ alkyl or phenyl optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₄ alkyl.

R ³ preferably represents one of the radicals mentioned under a), b), c), d) or e).

woπn

X for amino, hydroxy, mercapto, nitro, cyano, fluorine, chlorine, bromine, C _r C ₆ alkyl, C _r C ₄ haloalkyl, C _r C ₆ alkoxy, C _] -C ₄ haloalkoxy, C _r C ₆ - alkylthio, C _r C ₄ -haloalkylthio, C _r C ₆ -alkylsulfonyl, C _r C ₄ -haloalkylsulfonyl, C _r C ₆ -alkylcarbonyl, C _r C ₆ -alkoxycarbonyl, C _r C ₆ -alkylamino, Di- (C _r C ₆ alkyl) amino, aminocarbonyl, C _r C ₆ alkylaminocarbonyl, di (C ₁ -C ₆ alkyl) aminocarbonyl or C ₂ -C ₆ haloalkenylcarbonylamino and

Y and Z independently of one another for hydrogen, amino, hydroxy, mercapto,

Cyano, carboxyl, fluorine, chlorine, bromine, C _r C ₆ alkyl, C _r C ₄ haloalkyl, C _j -C ₆ alkoxy, C ₁ -C ₄ haloalkoxy, C _j -C ₈ alkylthio, C _] -C ₄ -Halogenal- kylthio, C _j -Cg alkylcarbonyl, C _j -C ₈ - alkoxycarbonyl, C _j -Cg alkylamino, di - ^ - Cg-alky ^ amino, Ci-Cg-alkylaminocarbonyl or Di ^ C _j -Cg-alkyl) - aminocarbonyl.

wonn

X and Y represent the meanings given above under a) as preferred for these substituents,

R ^{4 represents} hydrogen or C _r C ₄ alkyl and

worin gegebenenfalls eine Methylengruppe durch SO₂ ersetzt ist oder eine oder zwei nicht direkt benachbarte Methylengruppen durch Sauerstoff, Schwefel oder Stickstoff (welcher gegebenenfalls durch C_j-C₄-Alkyl, Phenyl oder Benzyl substituiert ist) ersetzt sind,n stands for 0, 1 or 2.

wherein is optionally replaced by a methyl group SO ₂ or (optionally substituted by which C _j -C ₄ alkyl, phenyl or benzyl) one or two not directly adjacent methylene groups by oxygen, sulfur or nitrogen are replaced,

represents 0 or 1,

m represents 0, 1, 2, 3, 4 or 5 and

W represents fluorine, chlorine, C _j -C ₈ alkyl or optionally substituted by fluorine, chlorine, bromine, C _r C ₄ alkyl, C _r C ₄ haloalkyl, C _r C ₄ alkoxy or C _r C ₄ -Halo- genalkoxy substituted phenyl.

d) In each case optionally substituted by fluorine, chlorine, bromine, C _ι -C ₄ alkyl or by optionally fluorine-, chlorine-, C ₁ -C ₄ alkyl, C _j -C ₄ haloalkyl, C _j - C ₄ - alkoxy, or C _j -C ₄ haloalkoxy substituted phenyl substituted pyridyl-C _r C ₂ alkyl, furanyl C ₁ -C ₂ alkyl or thienyl-C _r C ₂ alkyl.

e) In each case optionally by fluorine, chlorine, bromine, C _j -C ^ alkyl or C _j -C ₄ -

Haloalkyl substituted pyridyl or benzthiazolyl.

R ¹ particularly preferably represents hydrogen or fluorine.

R ² particularly preferably represents hydrogen or C _j -C ₄ - alkyl.

R ³ particularly preferably represents one of the radicals mentioned under a), b), c), d) or e).

wonn

wonn

X for mercapto, nitro, cyano, fluorine, chlorine, bromine, C ₁ -C ₄ alkoxy, C _r C ₄ -

Haloalkoxy, C _r C ₄ -alkylthio, C _] -C ₄ -alkylsulfonyl, C _r C ₂ -haloalkylsulfonyl, C _r C ₄ -alkylcarbonyl, C _r C ₄ -alkylamino, di- (C _r C ₄ -alkyl) - amino, aminocarbonyl or C ₃ -C ₅ haloalkenylcarbonylamino and

Y and Z independently of one another for hydrogen, fluorine, chlorine, carboxyl,

C _r C ₄ alkyl, C _r C ₄ haloalkyl, C _r C ₂ alkylcarbonyl or C _r C ₄ alkoxycarbonyl.

wherein

X ^{1 represents} fluorine, chlorine or C _r C ₄ alkyl and

R ^{4 represents} hydrogen, methyl or ethyl.

worin für m ≠ 0 gegebenenfalls eine Methylengruppe durch SO₂, Sauer- stoff, Schwefel oder Stickstoff (welcher gegebenenfalls durch C_j-C₄- Alkyl oder Benzyl substituiert ist) ersetzt ist,

wherein for m ≠ 0 optionally one methylene group by SO _2, oxygen, sulfur or nitrogen (optionally substituted by C _j -C ₄ - substituted alkyl or benzyl) is replaced

1 represents 0 or 1 and

m stands for 0, 2 or 3.

d) optionally by fluorine, chlorine, methyl, ethyl or in each case by substituted by fluorine, chlorine or methyl phenyl furanylmethyl or pyridylmethyl. e) In each case optionally substituted by fluorine, chlorine, methyl, ethyl or trifluoromethyl pyridyl or benzthiazolyl.

R ¹ very particularly preferably represents fluorine.

R very particularly preferably represents hydrogen or methyl.

R ³ very particularly preferably represents one of the radicals mentioned under a), b), c), d) or e).

woπn

X for nitro, cyano, fluorine, chlorine, bromine, methoxy, trifiuormethoxy, methylthio, methylsulfonyl, ethyl sulfonyl, trifluoromethylsulfonyl, methylcarbonyl, aminocarbonyl or 3,4,4-trifluorobut-3-en-l-yl- carbonylamino stands,

Y and Z are independently hydrogen, fluorine, chlorine, carboxyl, methyl, ethyl, n-propyl, isopropyl or trifluoromethyl.

wherein

X ^{1 represents} chlorine and

R ^{4 represents} hydrogen or methyl.

A particularly emphasized group of compounds are those compounds of formula (I) in which R ^{3 represents} one of the radicals listed under a).

Another particularly emphasized group of compounds are those compounds of the formula (I) in which R represents one of the radicals listed under b).

Compounds of the formula (I) in which

R ^{3 represents} one of the radicals listed under c).

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 a combination of those listed as particularly preferred above

Meanings exist. 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 very 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) 3,4,4-trifluorobut-3-enoic acid chloride and 4-bromoaniline 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 amines of the formula (II) are reacted with acid chlorides of the formula (III), if appropriate in the presence of a diluent and, if appropriate, in the presence of a base.

The process according to the invention is preferably carried out in the presence of a diluent.

Suitable diluents are, in particular, organic solvents, for example optionally chlorinated aliphatic or aromatic hydrocarbons such as cyclohexane, toluene, xylene, dichloromethane, dichloroethane, chloroform or chlorobenzene, ethers such as diethyl ether, dioxane or tetrahydrofuran or

Nitriles such as acetonitrile.

Two-phase systems consisting of water and an organic solvent, for example water / methylene chloride or water / toluene, are also suitable as diluents. An excess of the amine of formula (II) used is also suitable as a diluent.

In principle, all organic or inorganic bases suitable for such acylation reactions can be used as the base.

Amines are preferably used, especially tertiary amines such as triethylamine, diazabicycloundecene (DBU), diazabicyclonones (DBN), diazabicycloctane (DABCO) or pyridine or alkali metal or alkaline earth metal carbonates, hydrogen carbonates or oxides. Sodium carbonate, potassium carbonate, sodium hydrogen carbonate and calcium oxide may be mentioned as examples.

The reaction temperature can be varied within a wide range. In general, temperatures between -20 ° C and 140 ° C, preferably between 0 ° C and 60 ° C.

The molar ratio of the compound of formula (II) to the compound of formula (III) is generally 2: 1 to 1: 2.

The reaction is generally carried out in the pressure range from 0.5 to 6 bar, but preferably under normal pressure.

For working up, for example, the reaction mixture is hydrolyzed, the product is extracted with an organic solvent such as ethyl acetate, dichloromethane or toluene and the organic phase is then concentrated.

The amines of the formula (II) required as starting materials are known and / or can be prepared in a simple manner by known methods.

The acid chlorides of the formula (III) required as starting materials are known (see, for example, US-5 389 680 and EP-432 861).

The compounds of the formula (I) can also be prepared by amines of the formula (II) with carboxylic acids of the formula (IV)

in welcher

in which

R ^{1 has} the meaning given above,

in the presence of a reactive auxiliary such as dicyclohexylcarbodiimide or carbonylbisimidazole in the presence of a diluent such as tetrahydrofuran, methylene chloride or acetonitrile (cf. Houben-Weyl, Methods of Organic Chemistry, Volume E5, p. 941 ff (1985)).

The active substances are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species 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 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. 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, for example Reticulitermes spp .. From the order of the anoplura, for example 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, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisisppia, Fpp., Phyllocnist spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonelliellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaella , 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 chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatordoderidisilimushimpphppm, spp. , Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,

Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera 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., Ctenocephalides felis.

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., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..

Plant-parasitic nematodes include e.g. 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 distinguished in particular by an excellent nematicidal action, for example against Meloidogyne incognita, and by a very good acaricidal action, for example against the common spider mite (Tetranychus urticae).

They have a systemic effect and can be applied over the leaf. They also have leaf insecticidal activity and activity against Pyricularia oryzae on rice.

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 dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers: for example ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granules are possible: eg broken and fractionated natural rocks such as caicit, 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; 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 ether, Al- kyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: eg 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 ones, can be used in the formulations

Phospholipids such as cephalins and lecithins and synthetic phospholipids. 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 of active compound, preferably between 0.5 and 90%.

The active substance according to the invention can be used in its commercially available formulations and in the use forms prepared from these formulations

Mixture with other active ingredients, 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.

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

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloroN- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyano-phenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S,

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

Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, 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, Flutolafosil, Fol-triafilosil, Flu- tri, Tri- Fthalides, fuberidazole, furalaxyl, furmecyclox, guazatine,

Hexachlorobenzene, Hexaconazole, Hymexazol, Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan, Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate,

Copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,

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

Ofurace, oxadixyl, oxamocarb, oxycarboxin,

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

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamid, tricyclazole, tridemorph, trifloriconol, trifloriconol, trifloriconol

Validamycin A, vinclozolin, zineb, ziram.

Bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamyan, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin,

Tecloftalam, copper sulfate and other copper preparations. Insecticides / acaricides / nematicides:

Abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alpha-methrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,

Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin,

Butyl pyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157

419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorofluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clochrinin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhex

Cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinone, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu- benzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,

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

Fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,

Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

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

Methami dophos, methidathione, methiocarb, methomyl, metolcarb, milbemectin,

Monocrotophos, moxidectin,

Naled, NC 184, NI 25, Nitenpyram,

Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,

Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos,

Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos,

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

Quinalphos, RH 5992,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio-methon, Thionazine, Thuringiensin, Tralomenhroniazonium, Tronomenophoniazonium Tronomonhronizonium Tronomonophoniazonium Tronomoshronizonium Tronomonophonizonium Tronomonophonium Tronomonophonium Tronomonophonium Tronomonophonium Tronomoshronium Tronomonophonium Tronomonophonium Tronomoshronium Tronomonophonium Tronomonophonium Tronomoshronium Tronomonophonium Tronomoshronium Tronomonophonium Tronomonophonium Tronomonophonium Tronomonophonium Tronomonophonium Tronomidon 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-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice,

Hair lice, featherlings and fleas. These parasites include:

From the order of the Anoplurida, for example Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp .. From the order of the Mallophagida and the subordinates Amblycerina and Ischnocerina, for example Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp ..

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

From the order of the Siphonapterida 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 e.g. 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., Raillneu- spp., Pill monyssus spp., Sternostoma spp., Varroa spp ..

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp. Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes ss spnnpnn., OO Cvoddttt spnnpnn., .. LL Laaammmiiinnnnnosssiiinnonnpttt..eeesss ss spnnpnn. 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, buffalos, rabbits, chickens, turkeys, ducks,

Geese, bees, other pets such as Dogs, cats, house birds, aquarium fish and so-called experimental animals such as Infest hamsters, guinea pigs, rats and mice. By fighting these arthropods, deaths and reduced performance (in meat, milk, wool, skins, eggs, honey, etc.) are to be reduced, so that the use of the invention

Active ingredients a more economical and easier animal husbandry is possible.

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, the feed-through method, suppositories, by parenteral administration, such as Example by injections (intramuscular, subcutaneous, intravenous, intraperitonal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on) ), washing, powdering and with the help of shaped articles containing active ingredients such as necklaces, ear tags, tail tags, limb straps,

Halters, 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 as a chemical

Use bath.

The preparation and use of the active compounds according to the invention can be seen from the examples below. Manufacturing examples

example 1

23.8 g (0.15 mol) 3 are added dropwise to the solution of 19.1 g (0.15 mol) of 4-chloroaniline in 200 ml of dichloromethane and 15.2 g (0.15 mol) of triethylamine, with ice cooling and stirring. 4,4-trifluorobutene-3-acid chloride, dissolved in 40 ml dichloromethane. After stirring for 3 hours at 20 ° C., water is added, the organic phase is separated off, washed with dilute hydrochloric acid and then with water. After concentrating the organic phase in vacuo, the residue is stirred with petroleum ether, suction filtered and dried. 29.5 g of N- (4-chlorophenyl) -3,4,4-trifluorobutene-3-carboxamide of mp: 124 ° C. are obtained.

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

^klog p: Dekadischer Logarithmus des n-Octanol/Wasser- Verteilerkoeffizien¬ ten, bestimmt durch HPLC- Analytik an reversed phase mit

^k 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.

Application example

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 1, 5, 15, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27, 28 and 44 had an efficiency of 100 at an exemplary active ingredient concentration of 20 ppm %. Example B

Tetranychus test (OP-resistant / immersion treatment)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

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

Bean plants (Phaseolus vulgaris), which are heavily affected by all stages of development of the common spider mite Tetranychus urticae, are immersed in an active ingredient preparation of the desired concentration.

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

In this test e.g. the compounds according to Preparation Examples 1,

13 and 19 with an exemplary active ingredient concentration of 0.01%, an effect of at least 95% after 13 days.

Example C

Test with flies (Musca dornest! Ca)

Test animals: adult Musca domestica, Reichswald strain (OP, SP, carbamate-resistant)

Solvent: 35 parts by weight of ethyl englykolmonomethyl 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.

2 ml of this active ingredient preparation are pipetted onto filter paper dishes (Θ 9.5 cm), which are located in petri dishes of the appropriate size. After the filter discs have dried, 25 test animals are transferred to the Petri dishes and covered.

After 1, 3, 5 and 24 hours, the effectiveness of the active substance preparation is determined. 100% means that all flies have been killed; 0% means that no flies have been killed.

In this test, for example, the compound according to Preparation Example 12 showed an effectiveness of 100% at an exemplary concentration of 1000 ppm.

Example D

Test with fly larvae / development-inhibiting effect

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

[Dolls and adults (without contact to the active ingredient)]

Solvent: 35 parts by weight of ethyl englykolmonomethyl ether

Emulsifier: 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 meat (1 cm ³ ) 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 compounds according to Preparation Examples 6, 7, 8, 9, 10, 12, 13, 14, 15, 22, 29, 32, 33, 34, 44 and 55 showed an effect of at an exemplary active ingredient concentration of 1000 ppm 100% each. Example E

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, for example, the compounds according to Preparation Examples 3, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 25, 32, 33, 34, 36, 39, 40, 42 and 44 had one exemplary concentration of 20 μg / animal an effect of 100% each.

Example F

Cockroach test

Test animals: Periplaneta americana

Solvent: 35 parts by weight of ethylene glycol monomethyl ether emulsifier: 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.

2 ml of this active ingredient preparation are pipetted onto filter paper discs (0 9.5 cm), which are located in Petri dishes of the appropriate size. After the filter discs have dried, 5 test animals P. americana are transferred and covered.

After 3 days, the effectiveness of the active ingredient preparation is determined. The effectiveness is expressed in%. 100% means that all cockroaches have been killed; 0% means that no cockroaches have been killed.

In this test e.g. the compounds according to Preparation Examples 12 and 55 have an effectiveness of 100% in each case at an exemplary active ingredient concentration of 1000 ppm.

Claims

claims 1. Compounds of formula (I)

in which R ^{1 represents} hydrogen or halogen, R ^{2 represents} hydrogen, alkyl or phenyl which is optionally substituted by halogen or alkyl, R ³ for a) stands,

wherein X for amino, hydroxy, mercapto, nitro, cyano, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, alkylamino, dialkylamino, aminocarbonyl, alkylaminocarbonyl, Dialkylaminocarbonyl or haloalkenylcarbonylamino, Y and Z independently of one another for hydrogen, amino, hydroxy, mercapto, cyano, carboxyl, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylcarbonyl, alkoxycarbonyl, Alkylamino, dialkylamino, alkylaminocarbonyl or dialkylaminocarbonyl or b) stands,

woπn X and Y have the meaning given above, R> 4 represents hydrogen or alkyl and represents 0, 1, 2, 3 or 4 or c) stands

wherein 10 optionally a methylene group is replaced by SO ₂ or one or two not directly adjacent methylene groups in the ring are replaced by oxygen, sulfur or nitrogen (which is optionally substituted by alkyl, phenyl or benzyl), 15 represents 0, 1 or 2, m represents 0, 1, 2, 3, 4 or 5 and W represents halogen, alkyl or phenyl optionally substituted by halo, alkyl, haloalkyl, alkoxy or haloalkoxy, d) 5- or 6-membered hetarylalkyl optionally substituted by halogen, alkyl or by phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy or haloalkalkoxy is one to three heteroatoms from the series consisting of oxygen, sulfur and nitrogen or e) pyridyl or benzothiazolyl optionally substituted by halogen, alkyl or haloalkyl. 2. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that Amines of formula (II) HNR ² R ³ (II) in which R ² and R ^{3 have} the meaning given above, with acid chlorides of the formula (III)

in which R ^{1 has} the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a base. 3. pesticide, characterized by a content of at least one compound of formula (I) according to claim 1. 4. Use of compounds of formula (I) according to claim 1 for combating pests. 5. 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. 6. 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. 7. Use of compounds of formula (I) according to claim 1 for the preparation of pesticides.