WO1997002238A1

WO1997002238A1 - Fluorobutenoic acid hydrazones

Info

Publication number: WO1997002238A1
Application number: PCT/EP1996/002743
Authority: WO
Inventors: Udo Kraatz; Wolfram Andersch; Andreas Turberg; Norbert Mencke
Original assignee: Bayer Aktiengesellschaft
Priority date: 1995-07-05
Filing date: 1996-06-24
Publication date: 1997-01-23
Also published as: DE19524435A1; AU6415196A

Abstract

The invention pertains to new fluorobutenoic acid hydrazones of formula (I), wherein R1 is hydrogen or halogen and R?2 and R3¿ independently of each other are hydrogen, alkyl or in each case optionally substituted aryl or hetaryl or, together with the carbon atom to which they are bonded, form an in each case optionallysubstituted carbocyclic or heterocyclic ring. The invention also pertains to methods for preparing them and their use for animal pest control.

Description

Fluorobutenic acid hydrazones

The present invention relates to new fluorobutenic acid hydrazones, processes for their preparation and their use for controlling animal

Pests, in particular insects, arachnids and nematodes, which occur in agriculture, in the forests, in the protection of stocks and materials, and in the hygiene sector.

It has already become known that certain fluoroalkenyl compounds are effective as insecticides, acaricides and nematicides (cf. e.g. WO 92/15 555,

U.S. 4,952,590, U.S. 4,950,666, U.S. 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.

New fluorobutenic acid hydrazones of the formula (I) have now been found

in which

R ^{1 represents} hydrogen or halogen,

R ² and R ³ independently of one another represent hydrogen, alkyl or in each case optionally substituted aryl or hetaryl,

or

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

Depending on the nature of the substituents, the compounds of the formula (I) can be in the form of 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 further been found that the fluorobutenic acid hydrazones of the formula (I) are obtained when

A) hydrazones of the formula (II)

R ² R ³ C = N-NH ₂ (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,

or

B) acylhydrazines of the formula (IV)

in which

R ^{1 has} the meaning given above,

with carbonyl compounds of the formula (V)

O = CR ² R ³ (V) in which

R and R have the meaning given above,

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

Finally, it was found that the new fluorobutenic acid hydrazones of the formula

(I) have pronounced biological properties and are particularly suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in the forests, in the protection of stored products and materials and in the hygiene sector.

The fluorobutenic acid hydrazones according to the invention are generally defined by the formula (I).

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

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

R ² and R ³ independently of one another preferably represent hydrogen, C _j -C ^ -

Alkyl, optionally by fluorine, chlorine, bromine, nitro, cyano, amino, C _j - C ₆ alkyl, C _r C ₆ haloalkyl, C _r C ₆ alkoxy, C _r C ₆ haloalkoxy, C _r C ₆ - alkylthio, C ₁ -C ₆ haloalkylthio, C _j -C ₈ alkylamino or di-C _j -C ₈ - alkylamino-substituted phenyl or is optionally substituted by fluorine, chlorine, bromine or C _j -C ₄ alkyl-substituted hetaryl having 5 or 6

Ring atoms and one or two heteroatoms from the series nitrogen, oxygen and sulfur,

or

R ² and R ³ together with the carbon atom to which they are attached form a 4- to 9-membered ring which is optionally oxygen, sulfur or nitrogen (which is optionally substituted by C 1 -C ₈ -alkyl, phenyl or benzyl ) contains. R ¹ particularly preferably represents hydrogen or fluorine.

R ² and R ³ independently of one another particularly preferably represent hydrogen,

C ₁ -C ₆ alkyl, optionally by fluorine, chlorine, nitro, amino, CC ₄ -

Alkyl, CC ₄ -alkoxy, C _] -C ₄ -alkylamino or di-C ₁ -C ₄ -alkylamino-substituted phenyl or for each pyridyl, furanyl or thienyl optionally substituted by fluorine, chlorine, bromine or methyl,

or

R ² and R ³ together with the carbon atom to which they are attached form a 5- or 6-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.

In the radical definitions given above and below, hydrocarbon radicals, such as alkyl or alkenyl, are straight-chain or branched as far as possible, even in conjunction with heteroatoms such as alkoxy or alkylthio.

If, for example, 3,4,4-trifluorobut-3-ene acid chloride and 4-nitrobenzaldehyde hydrazone are used as starting materials in the preparation of compounds of the formula (I) according to process A), the course of the reaction can be represented by the following reaction scheme :

Is used in the preparation of compounds of formula (I) according to process B) e.g. 3,4,4-trifluorobut-3-enoyl-hydrazine and benzaldehyde as starting materials, the course of the reaction can be represented by the following reaction scheme:

CF ₂ = CF-CH ₂ - CONH-No-L OHC --c ^

Process A) described above for the preparation of compounds of the formula (I) is characterized in that hydrazones 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 .

Process A) according to the invention is preferably carried out in the presence of a diluent.

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

Two-phase systems consisting of water and an organic solvent, for example water / methylene chloride or water / toluene, are also suitable as diluents. 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 hydroxides. Examples include sodium carbonate, potassium carbonate, Sodium bicarbonate, sodium hydroxide, potassium hydroxide and calcium hydroxide called

The reaction temperature in process A) can be varied within a substantial range. In general, temperatures between -10 ° C and 180 ° C, preferably between 0 ° C and 100 ° C.

The molar ratio of the compound of formula (II) to the compound of formula (III) is generally 3 1 to 1 3, preferably 1.5 1 to 1 1.5

The reaction is generally carried out under normal pressure

For working up, for example, the reaction mixture is hydrolyzed and that

Product extracted with an organic solvent such as ethyl acetate, dichloromethane or toluene

Process B) described above for the preparation of compounds of the formula (I) is characterized in that acylhydrazines of the formula (IV) are reacted with carbonyl compounds of the formula (V), if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst

All customary solvents can be used as diluents in this process

Halogenated aliphatic or aromatic hydrocarbons such as cyclohexane, toluene, xylene, dichloromethane are preferably usable,

Chloroform, dichloroethane or chlorobenzene, alcohols such as methanol, ethanol or isopropanol, nitriles such as acetonitrile, ethers such as diisopropyl ether, tetrahydrofuran or dioxane or amides such as dimethylformamide In certain cases, the reaction can also be carried out without a solvent. In this case, it may be advantageous to use the carbonyl compound of the formula (V) in excess.

Examples of suitable catalysts are sulfonic acids such as p-toluenesulfonic acid.

The reaction temperatures can be varied within a wide range in process B) described above. In general, temperatures between 0 ° C and 160 ° C, preferably between 20 ° C and 130 ° C.

In general, in process B) the starting materials of the formulas (IV) and (V) are used in approximately equimolar amounts. However, it may be advantageous to use the carbonyl compound of the formula (III) in excess.

The reaction is generally carried out at normal pressure.

The reaction mixture is worked up in a conventional manner, for example by distilling off the diluent.

The hydrazones required as starting materials in production process A)

Formula (II) are known and / or can be prepared in a simple manner by known methods.

The hydrazones of the formula (II) are obtained, for example, if carbonyl compounds of the formula (V) are reacted with hydrazine.

The acid chlorides of the formula (III) required as starting materials in production process A) are known (see, for example, US Pat. No. 5,389,680 and EP-432,861).

The acylhydrazines of the formula (IV) required as starting materials in the preparation process B) can be prepared in a simple manner by reacting acid chlorides of the formula (III) with hydrazine or with tert-butyloxycarbonylhydrazine and subsequent acidic cleavage.

The carbonyl compounds of the formula (V) are generally known compounds of organic chemistry. 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 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, for example Eury gaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp. From the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigususpp. Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus s.

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 thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera sppi, Trichoplusia n. , Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella,

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., Chorioptes spp., Sarcoptes spp., Tarsonaia spp., Tarsonaia 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. They have a systemic effect and can be used on the leaf.

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, optionally using surface-active agents

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

If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. As a liquid solvent 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, for example petroleum fractions, mineral and vegetable oils, alcohols are essentially suitable , 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.

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 flours, 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 and

Granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks, as emulsifiers and / or foam-generating agents are possible, 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 dispersants 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, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90% The active substance 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 substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms and others

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, chlorozhalonolinolonolinolonolinolinolinothalonolinol, chlorothalonolinophenol

Cymoxanil, cyproconazole, cyprofuram,

Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone. Edifenphos, epoxyconazole, ethirimol, etridiazole,

Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, 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, hymexazole,

Imazaiil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodion, Isoprothiolan, Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxin copper and Bordeaux mixture, Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil, Nickel-dimethyldithiocarbamate, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixefuryloxoxuryl phthalide, pimaricin, piperalin, polycarbamates, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB), sulfur and sulfur preparations, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole Thicyofen

Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin, Triticonazol, Validamycin A, Vinclozolin, Zineb, Ziram.

Bactericides:

Bronopol, di chlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, AC 303 630, 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, 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, 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,

Methamidophos, 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, 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 furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active. The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms

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.

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

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

Pediculus spp., Phtirus spp., Solenopotes spp ..

From the order of the Mallophagida and the subordinates Amblycerina as well as I Isscchhnnoocceerriinnaa zz..BB .. .., LLeeDpiikkeennttrroonn SsDpDp ..., DDaammaalliinnaa SsDpDp ..., TTrriicchhooddeecctteess SspDDp ..., FFeelliiccoollaa s SpDpD.

From the order Diptera and the subordinates Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota ., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp.,

Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp ., Melophagus spp ..

From the order of the Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp .. From the order of the Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp ..

From the order of the Blattarida 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) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodterol spp ., 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, Lucilia cuprina and Musca domestica.

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, intraperitoneal, etc.), implant tate, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, powdering and with the help of active ingredient-containing shaped bodies such as collars , Ear tags, tail tags, limb bands, 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 and use of the active compounds according to the invention can be seen from the examples below.

Manufacturing examples

example 1

CF ₂ = CF-CH ₂ -CO-NH-N = CH

While cooling with ice, 4.8 g (30 mmol) of 3,4,4-trifluorobut-3-ene acid chloride, dissolved in 5 ml of dichloromethane, are added dropwise to a mixture of 5.0 g (30 mmol) of 4-nitrobenzaldehyde hydrazone in 60 ml dichloromethane and 2.8 g (33 mmol) sodium hydrogen carbonate in 30 ml water. After stirring overnight, the precipitate is filtered off, washed with water and recrystallized from ethyl acetate after drying.

3.5 g of 2-N- (4-nitrobenzylidene) -3,4,4-trifluorobut-3-ene acid hydrazide of

Mp: 204 ° C; Yield: 40.7% of theory.

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

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. Example (TV-D

CF ₂ = CF-CH ₂ -CO-NH-NH ₂ x CF ₃ COOH

A. (CH ₃ ) ₃ C-OC - NH-NH-CO-CH ₂ -CF = CF ₂

17.2 g (130 mmol) of tert-butyloxycarbonylhydrazine are placed in 200 ml of dichloromethane and mixed with a mixture of 12.6 g (150 mmol) of sodium hydrogen carbonate and 40 ml of water. A solution of 20.6 g (130 mmol) of 3,4,4-trifluorobutenoyl chloride in 40 ml of dichloromethane is added dropwise to this with stirring at 0-5 ° C. and the mixture is then stirred at 20 ° C. for 4 hours. The phases are separated, the organic phase is washed with water, dried and evaporated in vacuo.

30.4 g (92% of theory) of white crystals of mp: 88 ° C. are obtained.

B. CF ₂ = CF-CH ₂ -CO-NH-NH ₂ x CF ₃ COOH

14.0 g (55 mmol) of the compound obtained according to A. are dissolved in 40 ml of trifluoroacetic acid with ice cooling at 0-10 ° C. and stirred at 20 ° C. for 2 hours. Then excess trifiuoroacetic acid is removed in the

High vacuum.

18.7 g of fully crystallized crude product are obtained, which still contains excess trifluoroacetic acid. A small sample pressed on the clay plate shows an mp of 126-132 ° C.

Application example

Example A

Limit concentration test / nematodes

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

The active ingredient preparation is intimately mixed with soil that is heavily contaminated with the test nematodes. The concentration of the active ingredient in the preparation is practically irrelevant; the decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (= mg / 1) The treated soil is poured into pots and lettuce 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 degree of effectiveness of the active ingredient is determined in%. The degree of effectiveness is 100% if the infestation is avoided completely, 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, 5, 7 and 8 had an efficiency of 100% at an exemplary active ingredient concentration of 20 ppm. Example B

Test with Boophilus microplus resistant / SP resistant Parkhurst strain

Test animals: Adult suckled females

Solvent: Dimethyl sulf oxi d

20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide; lower concentrations are produced by dilution with 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 2, 5 and 7 showed an activity of 100% at an exemplary active ingredient concentration of 20 μg / animal.

Example C

Test with fly larvae / development-inhibiting effect

Test animals: Lucilia cuprina larvae (OP-resistant)

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

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol poly glycol ether

In order to produce a suitable formulation, 3 parts by weight of active ingredient are mixed with 7 parts of the solvent-emulsifier mixture mentioned above, and the emulsion concentrate thus obtained is diluted with water to the concentration desired in each case.

30 to 50 larvae per concentration are placed on horse meat (1 cm) 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 l'Λ times the development period (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 inhibitory effect means that no adult flies have hatched.

In this test, for example, the compound according to Preparation Example 7 showed an activity of 100% at an exemplary active ingredient concentration of 1000 ppm. Example D

Fly test / Musca domestica, strain WHO (N)

Solvent 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether

In order to produce a suitable formulation, 3 parts by weight are mixed

Active ingredient with 7 parts of the solvent-emulsifier mixture specified above and dilute the emulsion concentrate thus obtained with water to the desired concentration

2 ml of this active ingredient preparation are pipetted onto filter paper disks (0 9.5 cm), which are located in Petri dishes of the appropriate size. After drying the filter disks, 25 test animals are transferred to the Petri dishes and covered

After 6 hours, the effectiveness of the active substance preparation is determined. The effectiveness is expressed in%. 100% means that all the flies have been killed, 0% means that none of the flies have been killed

In this test, for example, the compound according to Preparation Example 7 showed an effectiveness of 100% at an exemplary active ingredient concentration of 1000 ppm.

Claims

claims

1. Compounds of formula (I)

CF = C-CH, - CONH - N = CR ² R ³

I, ⁽ 0

R

in which

R ^{1 represents} hydrogen or halogen,

R and R independently of one another represent hydrogen, alkyl or in each case optionally substituted aryl or hetaryl,

or

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

R ^{1 represents} hydrogen, fluorine, chlorine or bromine,

R ~ and R independently of one another for hydrogen, C _] -C ₁₂ alkyl, optionally by fluorine, chlorine, bromine, nitro, cyano, amino, C _j -C ₆ -

Alkyl, C ₁ -C ₆ haloalkyl, C _r C ₆ alkoxy, C _j -Cg haloalkoxy, CC ₆ alkylthio, C _j -C ₆ haloalkylthio, C _j -Cg alkyl amino or di-C ^ Cg alkylamino substituted phenyl or for optionally substituted by fluorine, chlorine, bromine or C _j -C ₄ alkyl substituted hetaryl with 5 or 6 ring atoms and one or two heteroatoms from the

Series of nitrogen, oxygen and sulfur are available,

or

R and R together with the carbon atom to which they are attached form a 4- to 9-membered ring which optionally contains oxygen, Contains sulfur or nitrogen (which is optionally substituted by C _j -C ₈ alkyl, phenyl or benzyl).

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

R ^{1 represents} hydrogen or fluorine,

R ² and R ³ are independently hydrogen, _C] -C ₆ - alkyl, if appropriate by fluorine, chlorine, nitro, amino, C ₁ -C ₄ alkyl, CC oxy ₄ -Alk-, C _j -C ₄ Alkylamino or di-C ₁ -C ₄ -alkylamino substituted phenyl or represent in each case optionally substituted by fluorine, chlorine, bromine or methyl pyridyl, furanyl or thienyl,

or

R and R together with the carbon atom to which they are attached form a 5- or 6-membered carbocycle.

4. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

A) hydrazones of the formula (II)

R ² R ³ C = N-NH ₂ (II)

in which

R and R have the meaning given in claim 1,

with acid chlorides of the formula (III)

in which

R ^{1 has} the meaning given in claim 1, if appropriate in the presence of a diluent and, if appropriate, in the presence of a base,

or

B) acylhydrazines of the formula (IV)

in which

R ^{1 has} the meaning given above,

with carbonyl compounds of the formula (V)

O = CR ² R ³ (V)

in which

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

5. pesticides, characterized by a content of at least one compound of the formula (I) according to claim 1.

6. Use of compounds of formula (I) according to claim 1 for combating pests.

7. 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.

8. 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.

9. Use of compounds of formula (I) according to claim 1 for the manufacture of pesticides.