Agents for combatting plant pests

0001The present invention relates to pesticides which comprise an active ingredient combination of the compound of the formula (I)<chemistry id="chem0001" num="0001"><img file="EP1593307B1_D0001.tif" /></chemistry>contained with fungicides.

0002Fungicidal active ingredients, such as azole derivatives, aryl benzyl ether, benzamides, morpholine compounds and other heterocycles, are known (cf. <nplcit id="ncit0001" npl-type="b"><text>KH Büchel "Plant Protection and Pest Control", pages 140 to 153, Georg Thieme-Verlag, Stuttgart 1977</text></nplcit>, <patcit id="pcit0001" dnum="EPOS0040345A"><text>EP-OS 0 040 345</text></patcit>, <patcit id="pcit0002" dnum="DEOS2324010A"><text>DE-OS 2 324 010</text></patcit>, <patcit id="pcit0003" dnum="DEOS2201063A"><text>DE-OS 2 201 063</text></patcit>, <patcit id="pcit0004" dnum="EPOS0112284A"><text>EP-OS 0 112 284</text></patcit>, <patcit id="pcit0005" dnum="EPOS0304758A"><text>EP-OS 0 304 758</text></patcit> and <patcit id="pcit0006" dnum="DDPS140412"><text>DD-PS 140 412</text></patcit>).

0003Mixtures of certain nitromethylene derivatives with fungicidal active ingredients and their use as pesticides in crop protection are already known (<patcit id="pcit0007" dnum="USP4731385P"><text>U.S. Patent 4,731,385</text></patcit>; <patcit id="pcit0008" dnum="JPOS6368507B"><text>JP-OS 63-68507</text></patcit>, <patcit id="pcit0009" dnum="JP63068505A"><text>63/68505</text></patcit>; <patcit id="pcit0010" dnum="JP63072608A"><text>63/72 608</text></patcit>; <patcit id="pcit0011" dnum="JP63072609A"><text>63/72 609</text></patcit>, <patcit id="pcit0012" dnum="JP63072610A"><text>63/72 610</text></patcit>, <patcit id="pcit0013" dnum="WO9603045A"><text>WO 96/03 045</text></patcit>, <patcit id="pcit0014" dnum="JP08245323B"><text>JP 08 245 323</text></patcit>, <patcit id="pcit0015" dnum="JP04368303A"><text>JP 04 368 303</text></patcit>, <patcit id="pcit0016" dnum="JP05017311A"><text>JP 05 017 311</text></patcit>, <patcit id="pcit0017" dnum="WO9722254A"><text>WO 97/22 254</text></patcit>, <patcit id="pcit0018" dnum="WO9221241A"><text>WO 92/21 241</text></patcit>). Mixtures of certain open-chain nitromethylenes and nitroguanidines with fungicides are already known (<patcit id="pcit0019" dnum="JPOS3047106B"><text>JP-OS 3047 106</text></patcit>; <patcit id="pcit0020" dnum="USP5181587P"><text>U.S. Patent 5,181,587</text></patcit>).

0004In <patcit id="pcit0021" dnum="JP04108704B"><text>JP 0410 8704</text></patcit>, <patcit id="pcit0022" dnum="WO9724032A"><text>WO 97/24032</text></patcit>, <patcit id="pcit0023" dnum="JP05039205B"><text>JP 0503 9205</text></patcit>, <patcit id="pcit0024" dnum="JP04112805B"><text>JP 0411 2805</text></patcit> and <patcit id="pcit0025" dnum="JP04120007B"><text>JP 0412 0007</text></patcit> Mixtures of the compound of formula (I) with other active ingredients, including certain fungicides, are described.

0005Mixtures of cyclopropylcarboxamides with certain nitromethylene or nitroguanidine derivatives are already known (<patcit id="pcit0026" dnum="JPOS3271207A"><text>JP-OS 3,271,207</text></patcit>).

0006Mixtures of, inter alia, imidacloprid and fungicidal active ingredients for use in material protection and against termites, but not for use against pests which damage plants, are already known (<patcit id="pcit0027" dnum="EPOS0511541A"><text>EP-OS 0 511 541</text></patcit>). Mixtures of imidacloprid and azolylmethylcycloalkanes, in particular triticonazole, are known from<patcit id="pcit0028" dnum="EPOS545834A"><text>EP-OS 545 834</text></patcit>.

0007However, it has not yet become known that the effects of nitroguanidine and certain azole derivatives mutually influence one another so favorably that, with good plant tolerance, they can be used in an excellent manner as control agents against plant pests.

0008The present invention relates to pesticides which comprise the compound of the formula (I)<chemistry id="chem0002" num="0002"><img file="EP1593307B1_D0002.tif" /></chemistry>contained in a mixture with the fungicidal active ingredients mentioned below.

0009The following may be mentioned as fungicides in the agents according to the invention for controlling plant pests:<ul id="ul0001" list-style="none"><li>(49) Compound of the formula<chemistry id="chem0003" num="0003"><img file="EP1593307B1_D0003.tif" /></chemistry></li></ul>

0010The active ingredient of formula (I) is from <patcit id="pcit0029" dnum="EPOS0375907A"><text>EP-OS 0 375 907</text></patcit> known.

0011The fungicidal active ingredients are also known.

0012For example, the following publications describe:<ol id="ol0001" compact="compact"><li>(1) compounds of the formula (II)<patcit id="pcit0030" dnum="DEOS2201063A"><text>DE-OS 2 201 063</text></patcit><patcit id="pcit0031" dnum="DEOS2324010A"><text>DE-OS 2 324 010</text></patcit><patcit id="pcit0032" dnum="DEOS2737489A"><text>DE-OS 2 737 489</text></patcit><patcit id="pcit0033" dnum="DEOS3018866A"><text>DE-OS 3,018,866</text></patcit><patcit id="pcit0034" dnum="DEOS2551560A"><text>DE-OS 2 551 560</text></patcit><patcit id="pcit0035" dnum="EP47594A"><text>EP 47 594</text></patcit><patcit id="pcit0036" dnum="DE2735872"><text>DE 2 735 872</text></patcit></li></ol>

0013In addition to the active ingredient of the formula (I), the active compound combinations according to the invention contain at least one fungicidal active ingredient selected from the compounds of group (1). They can also contain other active ingredients, as well as common auxiliaries and additives as well as diluents.

0014If the active compounds are present in the active compound combinations according to the invention in certain weight ratios, the mixtures show a clear synergistic effect. However, the weight ratios of the active ingredients in the active ingredient combinations can be varied within a relatively wide range. In general, 1 part by weight of active compound of the formula (I) 0.1 to 10 parts by weight, preferably 0.3 to 3 parts by weight of at least one fungicidal active ingredient from group (1).

0015The active compound combinations according to the invention have very good fungicidal properties. They can be used above all to control phytopathogenic fungi such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes etc.

0016The active compound combinations according to the invention are particularly suitable for combating cereal diseases, such as Erysiphe, Cochliobolus, Septoria, Pyrenophora and Leptosphaeria, and against fungal attack on vegetables, wine and fruit, for example against Venturia or Podosphaera on apples, Uncinula on vines or Sphaeroteca on cucumbers.

0017The active substance combinations are also very suitable for controlling animal pests, preferably arthropods, in particular insects, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are effective against normally sensitive and resistant species and against all or individual stages of development. The pests mentioned above include:

0018From the order of the Isopoda, for example Oniscus asellus, Annadillidium vulgare, Porcellio scaber.

0019From the order of the Diplopoda, for example, Blaniulus guttulatus.

0020From the order of the Chilopoda, for example Geophilus carpophagus and Scutigera spec.

0021From the order of the Symphyla, for example, Scutigerella immaculata.

0022From the order of the Thysanura, for example Lepisma saccharina.

0023From the order of the Collembola, for example Onychiurus armatus.

0024From the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

0025From the order of the Dermaptera, for example, Forficula auricularia.

0026From the order of the Isoptera, for example Reticulitermes spp ..

0027From the order of the anoplura, for example Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

0028From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.

0029From the order of the Thysanoptera, for example Hercinothrips femoralis, Thrips tabaci.

0030From the order of the Heteroptera, for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

0031From the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phoralosylumphum, spp. Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.

0032From the order of the Lepidoptera, for example 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., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera sppi, Trichoplapsia 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.

0033From the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa ​​decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephusppis, Atomilusinuspp 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., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

0034From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

0035From 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.

0036The fact that the active ingredient combinations are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

0037The active compound combinations according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations.

0038These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In the case of the use of water as an extender, for example 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 or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example Aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. The following are suitable as solid carriers: for example 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. Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Suitable emulsifying and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

0039Adhesives 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 also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

0040Dyes 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.

0041The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

0042The active compound combinations according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and also in mixtures with fertilizers or plant growth regulators.

0043The active substance combinations can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, soluble powders and granules.

0044They are used in the customary manner, for example by pouring, spraying, atomizing, scattering, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or incrusting.

0045When treating parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

0046In the seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

0047When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.

0048It has also been found that the active compound combinations according to the invention have a high insecticidal action against insects which destroy industrial materials.

0049The following insects may be mentioned by way of example and preferably, but without limitation:

0050Beetle like Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubis linearis, Lyctus pubis linearis, Lyctus pubis linearis, Lyctus pubescusis Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

0051Skin wings like Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

0052Termites like Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.

0053Solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agent.

0054The organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C. preferably used 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 oily solvents.

0055Mineral oils with a boiling range of 170 to 220 ° C, white spirit 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 ° C, turpentine oil and Like. Used.

0056In 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, are used.

0057The 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 also has an evaporation number 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.

0058According to a preferred embodiment, part of the organic chemical solvent or solvent mixture is replaced by an aliphatic polar organic chemical solvent or solvent mixture. Aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used.

0059In the context of the present invention, the known organic-chemical binders are the water-dilutable synthetic resins and / or synthetic resins which are 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 inden-coumarone resin, silicone resin, bristle tails such as Lepisma saccharina.

0060In 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.

0061The material to be protected against insect infestation is very particularly preferably wood and wood processing products.

0062Wood 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:

0063Lumber, 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.

0064The active substance combinations can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.

0065The 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 siccatives and UV stabilizers and, if appropriate Dyes and pigments and other processing aids.

0066The insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.

0067The amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimum amount of use 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 compound, based on the material to be protected.

0068An organic chemical solvent or solvent mixture and / or an oily or oil-like low-volatile organic chemical drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin are used as solvents and / or diluents.

0069The 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-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.

0070According 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 having an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.

0071All or part of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). 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).

0072The plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glycerol glycol or glycerol ether and p-toluenesulfonic acid ester.

0073Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone and ethylene benzophenone.

0074Water 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.

0075A particularly effective wood protection is achieved by industrial impregnation processes, such as vacuum, double vacuum or pressure processes.

0076The ready-to-use compositions may also contain other insecticides.

0077The insecticides mentioned in Wo 94/29 268 are particularly suitable as additional mixing partners. The compounds mentioned in this document are an integral part of the present application.

0078Insecticides such as chlorpyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron may be mentioned as particularly preferred mixing partners.

0079The good pesticidal activity of the active compound combinations according to the invention can be seen from the examples below. While the individual active substances or the known active substance combinations have weaknesses in the pesticidal activity, it is clear from the tables in the following examples that the activity found of the active substance combinations according to the invention is greater than the sum of the effects of the individual active substances and also greater than the effects of the known active substance combinations .

0080In the following examples, the active ingredient of the formula (I)<chemistry id="chem0004" num="0004"><img file="EP1593307B1_D0004.tif" /></chemistry>used.

0081The fungicidal active ingredients also used are given in the examples.