EP0880515A1

EP0880515A1 - Salts from imidazoline derivatives and their use as a parasite control agent

Info

Publication number: EP0880515A1
Application number: EP97902303A
Authority: EP
Inventors: Klaus Wagner; Christoph Erdelen
Original assignee: Bayer AG
Current assignee: Bayer CropScience AG
Priority date: 1996-02-14
Filing date: 1997-02-03
Publication date: 1998-12-02
Also published as: WO1997030043A1; JP2000504698A; KR100462768B1; US5994551A; CN1211245A; AU1599697A; TW338039B; BR9707518A; DE19605400A1; IL125633A0; KR19990077321A

Abstract

The present invention concerns new salts from imidazoline derivatives of the formula (I) in which R means hydrogen or alkyl, Y means nitro or cyano, W means a 5 or 6 membered heterocycle substituted as necessary and Z means an equivalent of an alkali metal, alkaline earth metal or an (NR1R2R3R4) grouping where R?1, R2, R3 and R4¿ are equal or different and mean hydrogen, alkyl, cycloalkyl optionally substituted, or benzyl optionally substituted, as well as their preparation and their use as a parasite control agent.

Description

SALTS OF IMIDAZOLIDE DERIVATIVES AND THEIR USE AS A PEST CONTROL

The present invention relates to new salts of imidazoline derivatives, a process for their preparation and their use for controlling animal

Pests

It is already known that certain alkylated imidazole in derivatives, such as l- (2-chloropyrimidin-5-yl) -3-methyl-2-nitroiminoimidazoline, have insecticidal properties (see e.g. EP-A 0 315 826). However, the effectiveness and range of action of these compounds is not always completely satisfactory, in particular at low application rates and concentrations.

New salts of imidazoline derivatives of the formula (I) have been found

in which

R represents hydrogen or alkyl,

Y represents nitro or cyano,

W represents an optionally substituted 5- or 6-membered heterocycle and

Z represents an equivalent of an alkali metal, alkaline earth metal or a [NR ¹ R ² R ³ R ⁴ ] grouping, where

R ¹ , R ² , R ³ and R ^{4 are the} same or different and are hydrogen,

Alkyl, optionally substituted cycloalkyl or optionally substituted benzyl

It has also been found that the salts of the imidazoline derivatives of the formula (I) are obtained if imidazolines of the formula (II) R

/ = λ

W-CH - N. NH (II)

N Y

in which

R, Y and W have the meaning given above,

with hydroxides of the formula (III)

Z-OH (III)

in which

Z has the meaning given above,

in the presence of a diluent

Finally, it was found that the new salts of imidazoline derivatives of the formula (I) have highly pronounced biological properties and, above all, for combating animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in the forests and in the stores - and material protection and occur in the hygiene sector, are suitable

The salts of imidazoline derivatives 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 preferably represents hydrogen or C _r C ₄ alkyl

Y preferably represents nitro or cyano

W preferably represents a 5- or 6-membered heterocycle which is optionally monosubstituted to trisubstituted identically or differently, the 1 or 2 Contains identical or different heteroatoms, such as preferably nitrogen, oxygen or sulfur atoms, where the substituents may be mentioned

Halogen, C _r C ₄ alkyl, C _r C ₄ alkoxy, C _r C ₄ haloalkyl, C _r C ₄ haloalkoxy, C, -C ₄ alkylthio, C _r C ₄ alkylsulfionyl, C _r C _4- alkylsulfonyl,

C _r C ₄ haloalkylthio, C _r C ₄ haloalkylsulfonyl, C _r C ₄ haloalkyl sulfonyl or C _r C ₂ alkenyl

Z preferably represents in each case one equivalent of lithium, sodium, potassium,

Rubidium, cesium, magnesium, calcium, ammonium, C _r C ₄ alkyl ammonium, di (C ₁ -C ₄ alkyl) ammonium, Tπ- (C _] -C ₄ alkyl) ammonium,

Tetra (C ₁ -C ₄ alkyl) ammonium, C ₅ or C ₆ cycloalkyl ammonium or

Dι- (C ₁ -C ₂ alkyl) benzyl ammonium

R particularly preferably represents hydrogen or methyl

Y particularly preferably represents nitro or cyano

W particularly preferably represents optionally substituted pyridyl,

Thiazolyl, oxazolyl, isothiazolyl or isoxazolyl, which may be mentioned as substituents

Fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, methyl sulfinyl or methyl sulfonyl

Z particularly preferably represents one equivalent of lithium, sodium,

Potassium, rubidium, cesium, magnesium, calcium, ammonium, methyl ammonium, dimethyl ammonium, tπ methyl ammonium, tetramethyl ammonium, tetraethyl ammonium, tetra-n-propyl ammonium, tetra-n-butyl ammonium or dimethyl benzyl ammonium

Preferred compounds according to the invention are substances of the formulas (IA) to

(ID)

m which

stands for the abovementioned general, preferred and particularly preferred meanings

The general definitions or explanations of residues or explanations given above or in preferred areas apply accordingly to the end products and to the starting and intermediate products. These residual definitions can be combined with one another, that is to say 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 - also in connection with heteroatoms such as alkoxy or alkylthio - are in each case straight-chain or branched as far as possible If, for example, 3H-1- (2-chloropyridin-5-yl) -2-nitroiminoimidazoline and lithium hydroxide are used as starting materials, the course of the reaction of the process according to the invention can be represented by the following reaction scheme:

The imidazolines of the formula (II) to be used as starting materials in the process according to the invention are known (see, for example, EP-A 0 259 738 and EP-A 0 315 826) and / or can be prepared by known methods (see, for example, the abovementioned references ).

The hydroxides of the formula (III) to be used as starting materials in the process according to the invention are generally known compounds.

The process according to the invention is carried out in the presence of a diluent. Water and organic / aqueous systems can preferably be used, it being possible to use all customary water-miscible organic solvents. Examples include ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; Nitriles, such as acetonitrile or propionitrile, and alcohols, such as methanol or ethanol.

The reaction temperatures can be varied within a wide range in the process according to the invention. In general, temperatures between 0 and 100 ° C, preferably between 0 and 60 ° C.

When carrying out the process according to the invention, 0.9 to 1.5 mol, preferably 0.95 to 1.2 mol or mol equivalent of a hydroxide of the formula (III) are generally employed per mol of imidazoline of the formula (II).

The end products are worked up and isolated in a generally known manner. In some cases it proves advantageous to use the compounds of the formula (III) in the form of their alcoholates.

With good plant tolerance and favorable warm blood toxicity, the active compounds are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored products and materials and in the hygiene sector. They can preferably be used as crop protection agents. They are active 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, for example Trichodectes spp., Damalinea spp. From the order of the Thysanoptera, for example 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, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Phemphrosusumpp., Pemphigususpp humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudocylcus 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 mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophana piferosellaella, pellellaella pianosella pellaella, Hofmannophila pseudosella , 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 psylloides, Tribolium spp., Agribiole spp., Tenebrio molitor. Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera, for example Diprion spp, Hoplocampa spp., Lasius spp, Monomorium pharaonis, Vespa spp From the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca ., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera 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 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 particularly notable for high insecticidal activity.

They can be used with particularly good success for combating plant-damaging insects, such as, for example, against the horseradish leaf beetle larvae (Phaedon cochlaeriae), the caterpillars of the cockroach (Plutella maculipennis), the green rice leafhopper (Nephotettix cinctriceps), and the caterpillars of the owl butterfly (Spodoptera) frugiperda) or the peach aphids (Mycus persicae).

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 prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents

If water is used as an extender, it is also possible, for example, to use organic solvents as liquid solvents. Liquid solvents are essentially: 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 such as butanol or glycol as well as 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

Solid carrier materials that come into question are, for example, ammonium salts and natural rock powder, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates, as solid carrier materials for Granules come into question, for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours, and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks, as emulsifiers - And / or foam-generating agents are possible. eg non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, eg alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates, and dispersants are, for example, lignin sulfitabi eyes and methyl cellulose

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

Active ingredient, preferably between 0.5 and 90%.

The active ingredient according to the invention can, in its commercially available formulations and in the use forms prepared from these formulations, in a mixture with other active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, regulate growth

Substances or herbicides are present. 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-dichloro-N- (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, di nocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,

Edifenphos, epoxyconazole, ethirimol, etridiazole,

Fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin,

Fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl aluminum, fthalide, fuberidazole, furaloxyl, furmecycl

Guazatine,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazole, 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,

Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Phthalid, Pimaricin, Piperahn,

Polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilone,

Quintozen (PCNB),

Sulfur and sulfur preparations, Tebuconazole, Tecloftalam, Tecnazen, Tetraconazole, Thiabendazole, Thicyofen, Thiophanat-methyl, Thiram, Toiclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflorolizol, Triflorolizol, Triflorolizol

Validamycin A, vinclozolin,

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, 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, 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, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,

Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon

HCH, heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, lvermectin, Lambda-cyhalothrin, Lufenuron,

Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,

Naled, NC 184, NI 25, Nitenpyram

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

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

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

From the order of the Siphonapterida 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., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,

Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus 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.

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

Sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, putti, 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 (for meat, milk, wool,

Hides, eggs, honey, etc.) can be reduced, so that by using the Active ingredients according to the invention a more economical and simple animal husbandry is possible

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

Method, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intrapeπtonal and others), 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 aid of shaped bodies containing active ingredients, such as collars, ear tags, tail tags, limb straps, 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 after Apply 100 to 10,000-fold dilution or use it as a chemical bath.

It has also been found that the compounds of the formula (I) according to the invention have a high insecticidal action against insects which destroy industrial materials

The following insects may be mentioned by way of example and preferably, but without limitation:

Beetle like

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linesces, spec monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec Dinoderus minutus

Hautflieger like

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur Teimites like

Kalotermes flavicolhs, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus

Bristle tail like Lepisma saccarina

In the present context, technical materials are to be understood as non-living materials, such as preferably plastics, adhesives, glues, papers and cartons, leather, wood and wood processing products and paints

The material to be protected against insect infestation is very particularly preferably wood and wood processing products

Wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are to be understood as examples. Lumber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood, chipboard, carpentry or wooden products that are generally used in house construction or joinery

The active compounds can be used as such, in the form of concentrates or generally customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes

The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellants, optionally desiccants and UV stabilizers and where appropriate, dyes and pigments and other processing aids

The insecticidal agent used to protect wood and wooden materials! or concentrates contain the active ingredient according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight The amount of the agents or concentrates used depends on the type and the occurrence of the insects and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active ingredient, based on the material to be protected.

An organic-chemical solvent or solvent mixture and / or an oily or oily low-volatility organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or water and / or water and optionally an emulsifier and / or wetting agent.

The organic chemical solvents used are preferably oily or oil-like solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C. Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oil-like solvents.

Mineral oils with a boiling range of 170 to 220 ° C, test gasoline with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° are advantageous C, turpentine oil and the like.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C. and / or locker oil and / or monochloronaphthalene, preferably α- Monochloronaphthalene used.

The organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture is also a Evaporation rate above 35 and one flash point above

30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture. According to a preferred embodiment, part of the organic-chemical solvent or solvent mixture or an ahphatic polar organic-chemical solvent or solvent mixture is replaced. Aliphatic organic-chemical solvents containing hydroxyl and / or ester and / or ether groups, such as for example, are preferably used Glycol ether, ester or the like for use

In the context of the present invention, the known organic-chemical binders are the water-dilutable synthetic resins and / or synthetic resins soluble or dispersible or emulsifiable in the organic chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders the basis of a natural and / or

Resin used

The synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellents, odor correctors tien and inhibitors or corrosion protection agents and the like are used

According to the invention, at least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder. Alkyd resins with an oil content of more than 45% by weight, preferably 50, are preferred according to the invention up to 68% by weight

All or part of the binder mentioned can be replaced by a fixative (gemιsch) or a plasticizer (gemιsch). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder

(based on 100% of the binder used) The plasticizers originate from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as Tπbutvl phosphate, adipic acid esters such as Dι- (2-ethylhexyi) adipate, stearates such as butyl stearate or amyl stearate or oleates such as butylglycol, oleates such as butylglycol, or oleates such as butylglycol, oleates such as butylglycol - Kolether, Glyceπnester and p-toluenesulfonic acid ester

Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone and ethylene benzophenone

Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants

A particularly effective wood protection is achieved by industrial processes, for example vacuum, double vacuum or pressure processes

The ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides

The additional admixing partners are preferably the insecticides and fungicides mentioned in WO 94/29 268. The compounds mentioned in this document are an express component of the present application

Insecticides, such as chloropyphosph, phoxime, silafluofin, alphamethin, cyfluthrin, cypermethrin, delta methin, permethrin, imidaclopd, NI-25, flufenoxuron, hexaflumuron, and hexoxlazoleuron, as well as fungus Azaconazole, propiconazole,

Tebuconazole, cyproconazole, metconazole, imazahl, dichlorfluanid, tolylfluanid, 3-iodo-2-propionyl-butylcarbamate, N-octyl-ιsothιazohn-3-one and 4,5-dichloro-N-octylιsothιazolιn-3-one

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

example 1

2.52 g (0.01 mol) of 3H-1- (2-chloropyridin-5-yl) -2-nitroimino-imidazoline and 0.24 g (0.01 mol) of lithium hydroxide are dissolved in 30 ml of water and briefly at

Room temperature stirred. The reaction solution is filtered and the filtrate is concentrated in vacuo. The residue is dried in vacuo over phosphorus pentoxide.

2.43 g (93% of theory) of the lithium salt of 3-H-1- (2-chloropyridin-5-yl) -2-nitroimino-imidazoline are obtained.

MS spectrum (according to the FAB method) *: MH ⁺ = 260.

[* BARREL: almost atomic bombardment]

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

Table 1

Examples of use

In the following application examples, the compound listed below is used as a reference substance:

Compound (A) known from EP-A 0 315 826

- (2-Chloropyridin-5-yl) -3-methyl-2-nitroimino-imidazoline

Example A

Phaedon larval test

Solvent 7 parts by weight of dimethylfomamide

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

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and with horseradish leaf beetle larvae

(Phaedon cochleariae) occupied while the leaves are still moist

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

In this test, at an exemplary active ingredient concentration of

0.01%, for example the compound according to preparation example 1 has a death rate of 90% and the compounds of preparation examples 2, 3, 4 and 5 have a death rate of 100% each after 7 days, while the known compound (A) only has one Showed a death rate of 10%

Example B

Plutella test

Solvent 7 parts by weight of dimethylformamide emulsifier 1 part by weight of alkylaryl polyglycol ether

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and with caterpillars being caterpillars

(Plutella maculipennis) occupied while the leaves are still moist.

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

In this test, at an exemplary active ingredient concentration of

0.1%, for example, the compounds according to Preparation Examples 2, 3, 4 and 5 had a death rate of 100% and the compound of Preparation Example 6 had a death rate of 85% each after 7 days, while the known compound (A) only showed a death rate of 25%

Example C

Spodoptera Frugiperda test

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

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

(Spodoptera frugiperda) occupied while the leaves are still moist

After the desired time is determined in%. 100% means that all the caterpillars have been killed, 0% means that none of the caterpillars have been killed

In this test, e.g. the compounds according to the preparation examples 1, 2, 3, 4, 5 and 6 at an exemplary active ingredient concentration of 0.1%

100% death after 7 days, while known compound (A) showed only 50% death

Example D

Nephotettix test

Rice seedlings (Oryza sativa) are treated by immersing them in the active ingredient preparation of the desired concentration and with larvae of the green rice leafhopper

(Nephotetüx cincüceps) when the seedlings are still moist

After the desired time, the death rate is determined in%. 100% means that all cicadas have been killed, 0% means that no cicadas have been killed

In this test, for example, the connections according to the preparation examples brought about

1, 2, 3, 4, 5 and 6 with an exemplary active ingredient concentration of 0.001%, a death rate of 100% after 6 days, while the known compound (A) only showed a death rate of 50%

Example E

Myzus persicae - sachet test

Solvent water, depending on the solubility acetone

A 0.1% stock solution was prepared from the active ingredients in the corresponding solvent. The corresponding test concentrations were diluted with a 15% sucrose solution in water

The respective active ingredient solution was pipetted into an artificial double membrane (= sachet) made of parafilm. the double membrane is drawn over a vessel in which there are 15 adult peach aphids (Mycus persicae). In this test procedure, the aphids absorb the active ingredient only orally

After the desired time, the death rate is determined in percent at different concentrations. The LC 50 values are calculated using probit analysis. The LC 50 value indicates the concentration at which 50% of the animals used are killed. The smaller the LC 50 value, the better the effect of the preparation

In this test, for example, the compounds of preparation examples 1, 2, 3, 4, 5 and 6 have LC 50 values between 0.006 ppm and 0.048 ppm after 2 days, while the known compound (A) has an LC 50 value of 0.15

Table E

(plant-damaging insects) Myzus persicae sachet test

^OO

Claims

claims

1 salts of imidazoline derivatives of the formula (I)

in which

R represents hydrogen or alkyl,

Y represents nitro or cyano,

W represents an optionally substituted 5- or 6-membered heterocycle and

R ¹ , R ² , R ³ and R ^{4 are the} same or different and represent hydrogen, alkyl, optionally substituted cycloalkyl or optionally substituted benzyl

2. Process for the preparation of the salts of the imidazoline derivatives of the formula (I),

in which

R represents hydrogen or alkyl,

Y stands for nitro or cyano. W represents an optionally substituted 5- or 6-membered heterocycle and

Z for an equivalent of an alkali metal, an alkaline earth metal or one

[NR ¹ R ² R ³ R ⁴ ] grouping, where

R ¹ , R ² , R ³ and R ^{4 are} identical or different and represent hydrogen, alkyl, optionally substituted cycloalkyl or optionally substituted benzyl,

characterized in that imidazolines of the formula (II)

in which

R, Y and W have the meaning given above,

with hydroxides of the formula (III),

Z-OH (III)

in which

Z has the meaning given above,

in the presence of a diluent

3. Pesticides, characterized by a content of at least one salt of an imidazoline derivative of the formula (I) according to claim 1

4. Use of salts of imidazoline derivatives of the formula (I) according to

Claim 1 for controlling pests

5 Process for combating pests, characterized in that salts of imidazoline derivatives of the formula (1) 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 salts of imidazoline derivatives of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active agents

7. Use of salts of imidazoline derivatives of the formula (I) according to

Claim 1 for the manufacture of pesticides