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="EP1593307A2_D0001.tif" /></chemistry> containing fungicides.

0002Fungicidal active compounds, such as azole derivatives, aryl benzyl ethers, benzamides, morpholine compounds and other heterocycles are known (see KH Büchel "Plant protection and pest control", pages 140 to 153, Georg Thieme Verlag, Stuttgart 1977, EP-OS 0 040 345 DE-OS 2 324 010, DE-OS 2 201 063, EP-OS 0 112 284, EP-OS 0 304 758 and DD-PS 140 412).

0003Mixtures of certain nitromethylene derivatives with fungicidally active compounds and their use as pesticides in crop protection are already known (US Pat. Nos. 4,731,385, 63/68507, 63/68505, 63/72608, 63/72 609, 63/72 610, US Pat. WO 96/03 045, JP 08 245 323, JP 04 368 303, JP 05 017 311, WO 97/22 254, WO 92/21 241). Mixtures of certain open-chain nitromethylenes and nitroguanidines with fungicides are already known (Japanese Laid-Open Application DOS 3,047,106, US Pat. No. 5,181,587).

0004JP 0410 8704, WO 97/24032, JP 0503 9205, JP 0411 2805 and JP 0412 0007 describe mixtures of the compound of the formula (I) with other active substances, including certain fungicides.

0005Mixtures of cyclopropylcarboxamides with certain Nitromethylenen- or Nitroguanidinderivaten are already known (JP-OS 3 271 207).

0006Mixtures of inter alia imidacloprid and fungicidal agents for use in the protection of materials and against termites, but not for use against plant-damaging pests are already known (EP-OS 0 511 541). Mixtures of imidacloprid and azolylmethylcycloalkanes, in particular triticonazole, are known from EP-OS 545 834.

0007However, it has not yet become known that nitroguanidine derivatives and certain azole derivatives influence each other so favorably that they can be used with good plant tolerance in an excellent manner as a control agent against plant pests.

0008The present invention relates to agents against plant pests containing the compound of formula (I)<chemistry id="chem0002" num="0002"><img file="EP1593307A2_D0002.tif" /></chemistry> in mixture with fungicidal active ingredients mentioned below.

0009As fungicides in the inventive compositions for controlling plant pests are mentioned:<ul id="ul0001" list-style="none"><li>(1) the azole derivative of the formula<chemistry id="chem0003" num="0003"><img file="EP1593307A2_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP1593307A2_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP1593307A2_D0005.tif" /></chemistry><chemistry id="chem0006" num="0006"><img file="EP1593307A2_D0006.tif" /></chemistry><chemistry id="chem0007" num="0007"><img file="EP1593307A2_D0007.tif" /></chemistry><chemistry id="chem0008" num="0008"><img file="EP1593307A2_D0008.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP1593307A2_D0009.tif" /></chemistry><chemistry id="chem0010" num="0010"><img file="EP1593307A2_D0010.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP1593307A2_D0011.tif" /></chemistry><chemistry id="chem0012" num="0012"><img file="EP1593307A2_D0012.tif" /></chemistry><chemistry id="chem0013" num="0013"><img file="EP1593307A2_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP1593307A2_D0014.tif" /></chemistry><chemistry id="chem0015" num="0015"><img file="EP1593307A2_D0015.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP1593307A2_D0016.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP1593307A2_D0017.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP1593307A2_D0018.tif" /></chemistry><chemistry id="chem0019" num="0019"><img file="EP1593307A2_D0019.tif" /></chemistry><chemistry id="chem0020" num="0020"><img file="EP1593307A2_D0020.tif" /></chemistry><chemistry id="chem0021" num="0021"><img file="EP1593307A2_D0021.tif" /></chemistry></li><li>(2) Azole derivatives of the formula<chemistry id="chem0022" num="0022"><img file="EP1593307A2_D0022.tif" /></chemistry></li><li>(3) the azole derivative of the formula<chemistry id="chem0023" num="0023"><img file="EP1593307A2_D0023.tif" /></chemistry></li><li>(4) the connection         S_X     (V)</li><li>(5) Azole derivative of the formula<chemistry id="chem0024" num="0024"><img file="EP1593307A2_D0024.tif" /></chemistry></li><li>(6) Heterocycles of the formula<chemistry id="chem0025" num="0025"><img file="EP1593307A2_D0025.tif" /></chemistry><maths id="math0001"><math display="block"><mrow><msup><mrow><mtext>(VII-1) X = O, R</mtext></mrow><mrow><mtext>8th</mtext></mrow></msup><msub><mrow><mtext> = CH</mtext></mrow><mrow><mtext>3</mtext></mrow></msub><msup><mrow><mtext>, R</mtext></mrow><mrow><mtext>9</mtext></mrow></msup><msup><mrow><mtext> = H, R</mtext></mrow><mrow><mtext>10</mtext></mrow></msup><msub><mrow><mtext> = C</mtext></mrow><mrow><mtext>10</mtext></mrow></msub><msub><mrow><mtext>H</mtext></mrow><mrow><mtext>21</mtext></mrow></msub><mspace linebreak="newline" /><mtext>(Tridemorph)</mtext></mrow></math><img file="EP1593307A2_D0026.tif" /></maths><maths id="math0002"><math display="block"><mrow><msup><mrow><mtext>(VII-2) X = O, R</mtext></mrow><mrow><mtext>8th</mtext></mrow></msup><msub><mrow><mtext> = CH</mtext></mrow><mrow><mtext>3</mtext></mrow></msub><msup><mrow><mtext>, R</mtext></mrow><mrow><mtext>9</mtext></mrow></msup><msup><mrow><mtext> = H, R</mtext></mrow><mrow><mtext>10</mtext></mrow></msup><msub><mrow><mtext> = C</mtext></mrow><mrow><mtext>9</mtext></mrow></msub><msub><mrow><mtext>H</mtext></mrow><mrow><mtext>19</mtext></mrow></msub><mspace linebreak="newline" /><mtext>(Aldimorph)</mtext></mrow></math><img file="EP1593307A2_D0027.tif" /></maths><chemistry id="chem0026" num="0026"><img file="EP1593307A2_D0028.tif" /></chemistry><chemistry id="chem0027" num="0027"><img file="EP1593307A2_D0029.tif" /></chemistry></li><li>(7) compound of the formula<chemistry id="chem0028" num="0028"><img file="EP1593307A2_D0030.tif" /></chemistry></li><li>(8) compound of the formula<chemistry id="chem0029" num="0029"><img file="EP1593307A2_D0031.tif" /></chemistry></li><li>(9) compound of the formula<chemistry id="chem0030" num="0030"><img file="EP1593307A2_D0032.tif" /></chemistry></li><li>(10) compound of the formula<chemistry id="chem0031" num="0031"><img file="EP1593307A2_D0033.tif" /></chemistry></li><li>(11) compound of the formula<chemistry id="chem0032" num="0032"><img file="EP1593307A2_D0034.tif" /></chemistry></li><li>(12) compound of the formula<chemistry id="chem0033" num="0033"><img file="EP1593307A2_D0035.tif" /></chemistry></li><li>(13) Compounds of the formula<chemistry id="chem0034" num="0034"><img file="EP1593307A2_D0036.tif" /></chemistry><chemistry id="chem0035" num="0035"><img file="EP1593307A2_D0037.tif" /></chemistry><chemistry id="chem0036" num="0036"><img file="EP1593307A2_D0038.tif" /></chemistry><chemistry id="chem0037" num="0037"><img file="EP1593307A2_D0039.tif" /></chemistry></li><li>(14) Compounds of the formula<chemistry id="chem0038" num="0038"><img file="EP1593307A2_D0040.tif" /></chemistry><maths id="math0003"><math display="block"><mrow><msup><mrow><mtext>(XV-1) R</mtext></mrow><mrow><mtext>12</mtext></mrow></msup><msub><mrow><mtext> = CH</mtext></mrow><mrow><mtext>3</mtext></mrow></msub><mspace linebreak="newline" /><mtext>(Pyrimethanil)</mtext></mrow></math><img file="EP1593307A2_D0041.tif" /></maths><maths id="math0004"><math display="block"><mrow><msup><mrow><mtext>(XV-2) R</mtext></mrow><mrow><mtext>12</mtext></mrow></msup><msub><mrow><mtext> = C C-CH</mtext></mrow><mrow><mtext>3</mtext></mrow></msub><mspace linebreak="newline" /><mtext>(Mepanipyrim)</mtext></mrow></math><img file="EP1593307A2_D0042.tif" /></maths></li><li>(15) Compounds of the formula<chemistry id="chem0039" num="0039"><img file="EP1593307A2_D0043.tif" /></chemistry><maths id="math0005"><math display="block"><mrow><msup><mrow><mtext>(XVI-1) R</mtext></mrow><mrow><mtext>13</mtext></mrow></msup><mtext>H =</mtext><mspace linebreak="newline" /><mtext>(Dichlofluanid)</mtext></mrow></math><img file="EP1593307A2_D0044.tif" /></maths><maths id="math0006"><math display="block"><mrow><msup><mrow><mtext>(XVI-2) R</mtext></mrow><mrow><mtext>13</mtext></mrow></msup><msub><mrow><mtext> = CH</mtext></mrow><mrow><mtext>3</mtext></mrow></msub><mspace linebreak="newline" /><mtext>(Tolylfluanid)</mtext></mrow></math><img file="EP1593307A2_D0045.tif" /></maths></li><li>(16) compound of the formula<chemistry id="chem0040" num="0040"><img file="EP1593307A2_D0046.tif" /></chemistry></li><li>(17) compound of the formula<chemistry id="chem0041" num="0041"><img file="EP1593307A2_D0047.tif" /></chemistry></li><li>(18) compound of the formula<chemistry id="chem0042" num="0042"><img file="EP1593307A2_D0048.tif" /></chemistry></li><li>(19) compound of the formula<chemistry id="chem0043" num="0043"><img file="EP1593307A2_D0049.tif" /></chemistry></li><li>(20) compound of the formula<chemistry id="chem0044" num="0044"><img file="EP1593307A2_D0050.tif" /></chemistry></li><li>(21) Compound of the formula<chemistry id="chem0045" num="0045"><img file="EP1593307A2_D0051.tif" /></chemistry></li><li>(22) Compound of formula<chemistry id="chem0046" num="0046"><img file="EP1593307A2_D0052.tif" /></chemistry></li><li>(23) compound of the formula<chemistry id="chem0047" num="0047"><img file="EP1593307A2_D0053.tif" /></chemistry></li><li>(24) Compounds of the formula         Cl₃CSR¹⁴     (XXV)<chemistry id="chem0048" num="0048"><img file="EP1593307A2_D0054.tif" /></chemistry><chemistry id="chem0049" num="0049"><img file="EP1593307A2_D0055.tif" /></chemistry></li><li>(25) compound of the formula<chemistry id="chem0050" num="0050"><img file="EP1593307A2_D0056.tif" /></chemistry></li><li>(26) compound of the formula<chemistry id="chem0051" num="0051"><img file="EP1593307A2_D0057.tif" /></chemistry></li><li>(27) compound of the formula<chemistry id="chem0052" num="0052"><img file="EP1593307A2_D0058.tif" /></chemistry></li><li>(28) compound of the formula<chemistry id="chem0053" num="0053"><img file="EP1593307A2_D0059.tif" /></chemistry></li><li>(29) Compound of the formula<chemistry id="chem0054" num="0054"><img file="EP1593307A2_D0060.tif" /></chemistry></li><li>(30) compound of the formula<chemistry id="chem0055" num="0055"><img file="EP1593307A2_D0061.tif" /></chemistry></li><li>(31) Compound of formula<chemistry id="chem0056" num="0056"><img file="EP1593307A2_D0062.tif" /></chemistry></li><li>(32) Compounds of the formula<chemistry id="chem0057" num="0057"><img file="EP1593307A2_D0063.tif" /></chemistry><maths id="math0007"><math display="block"><mrow><mtext>(XXXIII-1) M = Zn</mtext><mspace linebreak="newline" /><mtext>(Zineb)</mtext></mrow></math><img file="EP1593307A2_D0064.tif" /></maths><maths id="math0008"><math display="block"><mrow><mtext>(XXXIII-2) M = Mn</mtext><mspace linebreak="newline" /><mtext>(Maneb)</mtext></mrow></math><img file="EP1593307A2_D0065.tif" /></maths><maths id="math0009"><math display="block"><mrow><mtext>(XXXIII-3) M = Mn / Zn</mtext><mspace linebreak="newline" /><mtext>(Mancozeb)</mtext></mrow></math><img file="EP1593307A2_D0066.tif" /></maths></li><li>(33) Compound of the formula<chemistry id="chem0058" num="0058"><img file="EP1593307A2_D0067.tif" /></chemistry></li><li>(34) Compound of the formula<chemistry id="chem0059" num="0059"><img file="EP1593307A2_D0068.tif" /></chemistry></li><li>(35) Compound of the formula<chemistry id="chem0060" num="0060"><img file="EP1593307A2_D0069.tif" /></chemistry></li><li>(36) compound of the formula<chemistry id="chem0061" num="0061"><img file="EP1593307A2_D0070.tif" /></chemistry></li><li>(37) Compound of formula<chemistry id="chem0062" num="0062"><img file="EP1593307A2_D0071.tif" /></chemistry></li><li>(38) Compounds of the formula<chemistry id="chem0063" num="0063"><img file="EP1593307A2_D0072.tif" /></chemistry>    in which    R¹⁵ and R¹⁶ independently of one another represent hydrogen, halogen, methyl or phenyl and    R¹⁷ is hydrogen or methyl,</li><li>(39) 8-^tButyl 2- (N-ethyl-Nn-propylamino) -methyl-1,4-dioxaspiro [4,5] decane of the formula<chemistry id="chem0064" num="0064"><img file="EP1593307A2_D0073.tif" /></chemistry></li><li>(40) compound of the formula<chemistry id="chem0065" num="0065"><img file="EP1593307A2_D0074.tif" /></chemistry></li><li>(41) Compound of the formula<chemistry id="chem0066" num="0066"><img file="EP1593307A2_D0075.tif" /></chemistry></li><li>(42) Compound of the formula<chemistry id="chem0067" num="0067"><img file="EP1593307A2_D0076.tif" /></chemistry><chemistry id="chem0068" num="0068"><img file="EP1593307A2_D0077.tif" /></chemistry><chemistry id="chem0069" num="0069"><img file="EP1593307A2_D0078.tif" /></chemistry><chemistry id="chem0070" num="0070"><img file="EP1593307A2_D0079.tif" /></chemistry></li><li>(43) Compound of the formula<chemistry id="chem0071" num="0071"><img file="EP1593307A2_D0080.tif" /></chemistry></li><li>(44) Benzimidazole of the formula<chemistry id="chem0072" num="0072"><img file="EP1593307A2_D0081.tif" /></chemistry> R⁹ = CONHtBu; R⁶ = -NHCOOMe benomyl<chemistry id="chem0073" num="0073"><img file="EP1593307A2_D0082.tif" /></chemistry>    R⁹ = H; R⁶ = -NHCOOMe carbendazine</li><li>(45) compound of the formula<chemistry id="chem0074" num="0074"><img file="EP1593307A2_D0083.tif" /></chemistry></li><li>(46) Compound of the formula<chemistry id="chem0075" num="0075"><img file="EP1593307A2_D0084.tif" /></chemistry></li><li>(47) Compound of formula<chemistry id="chem0076" num="0076"><img file="EP1593307A2_D0085.tif" /></chemistry></li><li>(48) Compound of the formula<chemistry id="chem0077" num="0077"><img file="EP1593307A2_D0086.tif" /></chemistry></li><li>(49) compound of the formula<chemistry id="chem0078" num="0078"><img file="EP1593307A2_D0087.tif" /></chemistry></li></ul>

0010The active ingredient of the formula (I) is known from EP-OS 0 375 907.

0011The fungicidal agents are also known.

0012For example, the following publications describe:

(1) Compounds of the formula (II)

0013<ul id="ul0002" list-style="none" compact="compact"><li>DE-OS 2 201 063</li><li>DE-OS 2 324 010</li><li>DE-OS 2 737 489</li><li>DE-OS 3,018,866</li><li>DE-OS 2 551 560</li><li>EP 47 594</li><li>DE 2 735 872</li></ul>

0014The active compound combinations according to the invention contain, in addition to the active ingredient of the formula (I), at least one fungicidal active substance selected from the compounds of group (1). In addition, they may also contain other active ingredients as well as customary auxiliaries and additives as well as diluents.

0015Preferred fungicidal active substances in the compositions according to the invention are: tebuconazole, triadimenol, cyproconazole.

0016If the active ingredients in the active compound combinations according to the invention are present in certain weight ratios, a clear synergistic effect of the mixtures is shown. However, the weight ratios of the active ingredients in the drug 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 substance from the group (1).

0017The active compound combinations according to the invention have very good fungicidal properties. They can be used especially for controlling phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes, etc.

0018The 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.

0019The active compound 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 products and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The above mentioned pests include:<ul id="ul0003" list-style="none"><li>From the order of the Isopoda eg Oniscus asellus, Armadillidium vulgare, Porcellio scaber.</li><li>From the order of Diplopoda eg Blaniulus guttulatus.</li><li>From the order of Chilopoda eg Geophilus carpophagus, Scutigera spec.</li><li>From the order of Symphyla eg Scutigerella immaculata.</li><li>From the order of Thysanura eg Lepisma saccharina.</li><li>From the order of the Collembola eg Onychiurus armatus.</li><li>From the order of Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.</li><li>From the order of the Dermaptera eg Forficula auricularia.</li><li>From the order of the Isoptera eg Reticulitermes spp ..</li><li>From the order of Anoplura eg Pediculus humanus corporis, Haematopinus spp., Linognathus spp.</li><li>From the order of Mallophaga eg Trichodectes spp., Damalinea spp.</li><li>From the order of Thysanoptera eg Hercinothrips femoralis, Thrips tabaci.</li><li>From the order of Heteroptera eg Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.</li><li>From the order of Homoptera eg Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Phylloxera vastatrix, Pemphigus spp. Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.</li><li>From the order of Lepidoptera eg 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, Pani's flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., 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.</li><li>From the order of Coleoptera eg Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa ​​decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus 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.</li><li>From the order of Hymenoptera eg Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.</li><li>From the order of Diptera eg 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., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.</li></ul>

0020The good plant compatibility of the active compound combinations in the concentrations necessary for controlling plant diseases allows a treatment of aboveground plant parts, of plant and seed, and the soil.

0021The 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, as well as ULV formulations.

0022These formulations are prepared in a known manner, eg by mixing the active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, for example also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes 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. By liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, eg Aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: for example Cracked and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Suitable emulsifying and / or foam-producing agents are: for example nonionic 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 hydrolysates. Suitable dispersants are: for example Lignin-sulphite liquors and methylcellulose.

0023Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives may be mineral and vegetable oils.

0024Dyes such as inorganic pigments such as 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.

0025The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%.

0026The 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 in mixtures with fertilizers or plant growth regulators.

0027The active compound 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.

0028The application is carried out in a customary manner, for example by casting, spraying, spraying, scattering, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or encrusting.

0029In the treatment of parts of plants, the drug concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001 wt .-%, preferably between 0.5 and 0.001%.

0030In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g are needed.

0031When treating the soil, drug concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.

0032In addition, it has been found that the active compound combinations according to the invention show a high insecticidal activity against insects which destroy industrial materials.

By way of example and preferably without limiting however, the following insects are mentioned:

Beetle like

0033Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

Hymenoptera like

0034Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites like

0035Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.

0036Solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agent.

0037As organic-chemical solvents are preferably oily or oily solvents having an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C used. As such low-volatility, water-insoluble, oily and oily solvents corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene are used.

0038Mineral oils having a boiling range of 170 to 220 ° C., white spirit having a boiling range of 170 to 220 ° C., spindle oil having a boiling range of 250 to 350 ° C., petroleum or aromatic compounds having a boiling range of 160 to 280 ° C., turpentine oil and Like. For use.

0039In a preferred embodiment, liquid aliphatic hydrocarbons having a boiling range of from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons having a boiling range from 180 to 220 ° C. and / or spindle oil and / or monochloromonaphthalene, preferably α-monochloronaphthalene, are used.

0040The organic low-volatile 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 light or medium volatility organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number above 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.

0041In a preferred embodiment, a portion of the organic chemical solvent or solvent mixture is replaced by an aliphatic polar organic chemical solvent or solvent mixture. Preferably, aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups are used, for example glycol ethers, esters or the like.

0042In the context of the present invention, the organic-chemical binders which are known per se are water-dilutable and / or soluble or dispersible in the organic-chemical solvents used or emulsifiable synthetic resins and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, eg Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene cumarone resin, silicone resin, bristle tails such as Lepisma saccharina.

0043Technical materials in the present context are non-living materials, such as preferably plastics, adhesives, glues, paper and cardboard, leather, wood and woodworking products and paints.

0044Most preferably, the material to be protected from insect attack is wood and woodworking products.

0045By wood and woodworking products, which can be protected by the composition according to the invention or mixtures containing it, is to be understood by way of example: Timber, wooden beams, railway sleepers, bridge parts, boat jetties, wooden vehicles, crates, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood, chipboard, carpentry or wood products, which are generally used in home construction or joinery.

0046The active compound combinations can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.

0047The formulations mentioned can be prepared in a manner known per se, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersing and / or binding or fixing agent, water repellent, optionally siccatives and UV stabilizers and optionally Dyes and pigments and other processing aids.

0048The insecticidal agents or concentrates used for the protection of wood and wood-based materials contain the active ingredient according to the invention in a concentration of 0.0001 to 95 wt .-%, in particular 0.001 to 60 wt .-%.

0049The amount of agents or concentrates used depends on the nature and occurrence of the insects and on the medium. The optimal amount used 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.

0050The solvent and / or diluent used is an organic-chemical solvent or solvent mixture and / or an oily or oily, volatile organic-chemical drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin used.

0051The synthetic resin used as the binder may 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 and inhibitors or corrosion inhibitors and the like can be used.

0052According to the invention, at least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably present as the organic-chemical binder in the middle or in the concentrate. Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.

0053The mentioned binder can be completely or partially 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. Preferably, they replace 0.01 to 30% of the binder (based on 100% of the binder used).

0054The plasticizers are derived from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric 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, glycerol ethers or higher molecular weight glycol ethers, glycerol esters and p-toluenesulfonic acid ester.

0055Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.

0056Particularly suitable solvents or diluents are also water, optionally in admixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersants.

0057A particularly effective wood protection is achieved by large-scale impregnation, eg vacuum, double vacuum or printing process.

0058The ready-to-use agents may optionally contain further insecticides.

0059As additional Zumischpartner preferably come in Wo 94/29 268 mentioned insecticides in question. The compounds mentioned in this document form an integral part of the present application.

0060Very particularly preferred admixing partners are insecticides such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron.

0061The good pesticidal activity of the active compound combinations according to the invention is evident from the following examples. While the individual active compounds or the known drug combinations in the pesticidal activity have weaknesses, it is clear from the tables of the following examples that the found effect of the active compound combinations according to the invention is greater than the sum of the effects of the individual drugs and also greater than the effects of the known drug combinations ,

0062In the following examples, the active ingredient of the formula (I)<chemistry id="chem0079" num="0079"><img file="EP1593307A2_D0088.tif" /></chemistry> used.

0063The fungicidal active ingredients also used are given in the examples.

<b>Example A</b>

Plutella Test

0064Solvent: 7 parts by weight of dimethylformamide<dl id="dl0001" compact="compact"><dt>emulsifier:</dt><dd>1 Part by weight of alkylaryl polyglycol ether</dd></dl>

0065To prepare a suitable preparation of active compound, 1 part by weight of an active ingredient or a combination of active ingredients with the specified amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

0066Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the cabbage (Plutella xylostella) while the leaves are still moist.

0067After the desired time the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

0068In this test, for example, the following active substance combinations according to the present application show a synergistically enhanced activity in comparison to the individually used active substances:<tables id="tabl0001" num="0001"><img file="EP1593307A2_D0089.tif" /></tables>

<b>Example B</b>

Limiting concentration test / soil insects

0069<dl id="dl0002" compact="compact"><dt>Test insect:</dt><dd>Spodoptera frugiperda</dd><dt>Solvent:</dt><dd>4 Parts by weight acetone</dd><dt>emulsifier:</dt><dd>1 Part by weight of alkylaryl polyglycol ether</dd></dl>

0070To prepare a suitable preparation of active compound, 1 part by weight of the active substance or of the active substance mixture is mixed with the specified amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

0071The preparation of active compound is intimately mixed with soil. In this case, the concentration of the active ingredient in the preparation plays virtually no role, the only decisive factor is the amount of active ingredient or active substance mixture weight per unit volume of soil, which is stated in ppm (mg / l).

0072Fill soil in 0.5 1 pots and leave them at 20 ° C. Immediately after preparation 3 pre-germinated maize kernels are laid out per pot. After emergence of the corn kernels, drill sleeves are placed on the pots. 9 days after the beginning of the corn is occupied with the test insects. After another 5 days, the degree of kill is determined in%. 100% means that all test insects have been killed; 0% means that just as many insects live as in the untreated control.

0073In this test, for example, the following active substance combinations according to the present application show a synergistically enhanced activity in comparison to the individually used active substances:<tables id="tabl0002" num="0002"><img file="EP1593307A2_D0090.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP1593307A2_D0091.tif" /></tables>

<b>Example C</b>

Boundary concentration test / root systemic effect

0074<dl id="dl0003" compact="compact"><dt>Test insect:</dt><dd>Phaedon cochleariea larvae</dd><dt>Solvent:</dt><dd>4 Parts by weight acetone</dd><dt>emulsifier:</dt><dd>1 Part by weight of alkylaryl polyglycol ether</dd></dl>

0075To prepare a suitable preparation of active compound, 1 part by weight of the active substance or of the active substance mixture is mixed with the specified amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

0076The preparation of active compound is intimately mixed with soil. In this case, the concentration of the active ingredient in the preparation plays virtually no role, the only decisive factor is the amount of active ingredient or active substance mixture weight per unit volume of soil, which is stated in ppm (mg / l).

0077Fill soil in 250 ml pots and plant them with cabbage (Brassica oleracea). The active ingredient or combination of active ingredients can thus be absorbed by the plant roots from the soil and transported into the leaves.

0078After 7 days, the leaves are filled with the above test animals. After another 3 days, the degree of kill is determined in%. 100% means that all test insects have been killed; 0% means that just as many insects live as in the untreated control.

0079In this test, for example, the following active substance combinations according to the present application show a synergistically enhanced activity in comparison to the individually used active substances:<tables id="tabl0004" num="0004"><img file="EP1593307A2_D0092.tif" /></tables>

<b>Example D</b>

Calculation formula for the efficiency of a combination of two active substances

0080The expected effect for a given combination of two drugs may be (see Colby, SR, "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds <u>15</u>, Pages 20-22, 1967) are calculated as follows:

0081If<dl id="dl0004"><dt>X</dt><dd>the efficiency, expressed in% of the untreated control, when using the active substance A at a rate of <u>m</u> g / ha</dd><dt>Y</dt><dd>the efficiency, expressed in% of the untreated control, when using the active substance B in an application rate of <u>n</u> g / ha</dd><dt>e</dt><dd>the efficiency, expressed in% of the untreated control, when using the active compounds A and B in application rates of <u>m</u> and <u>n</u> g / ha means</dd></dl> then<maths id="math0010"><math display="block"><mrow><mtext mathvariant="italic">e</mtext><mtext> = </mtext><mtext mathvariant="italic">X</mtext><mtext> + </mtext><mtext mathvariant="italic">Y</mtext><mtext> - </mtext><mfrac><mrow><mtext mathvariant="italic">X x Y</mtext></mrow><mrow><mtext mathvariant="italic">100</mtext></mrow></mfrac></mrow></math><img file="EP1593307A2_D0093.tif" /></maths>

0082If the actual fungicidal effect is greater than calculated, the combination is over-additive in its effect, ie there is a synergistic effect. In this case, the actual observed efficiency must be greater than the value for the expected efficiency (E) calculated from the above formula.

Phytophthora text (tomato) / protective

0083<dl id="dl0005" compact="compact"><dt>Solvent:</dt><dd>47 Parts by weight acetone</dd><dt>emulsifier:</dt><dd>3 Parts by weight of alkylaryl polyglycol ether</dd></dl>

0084To produce a suitable preparation of active compound, 1 part by weight of the active ingredient or of the active ingredient mixture with the specified amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration, or it dilutes a commercial formulation of active ingredient or drug combination with water to the desired concentration.

0085To test for protective activity, young plants are sprayed with the commercial preparation of active compound in the stated application rate. After the spray coating has dried, the plants are treated with an aqueous spore suspension of<i><b>Phytophthora infestans</b></i> inoculated. The plants are then placed in an incubation booth at about 20 ° C and 100% relative humidity.

00863 Days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

0087From the table below it is clear that the effect found of the active compound combinations according to the invention is greater than the calculated (see above), ie that a synergistic effect is present.<tables id="tabl0005" num="0005"><img file="EP1593307A2_D0094.tif" /></tables>

<b>Example E</b>

Sphaerotheca test (cucumber) / protective

0088<dl id="dl0006"><dt>Solvent:</dt><dd>47 Parts by weight acetone</dd><dt>emulsifier:</dt><dd>3 Parts by weight of alkylaryl polyglyleneol ether</dd></dl>

0089To produce a suitable preparation of active compound, 1 part by weight of the active ingredient or of the active ingredient mixture with the specified amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration, or it dilutes a commercial formulation of active ingredient or drug combination with water to the desired concentration.

0090To test for protective activity, young plants are sprayed with the commercial preparation of active compound in the stated application rate. After the spray coating has dried, the plants are treated with an aqueous spore suspension of<i><b>Sphaerotheca fuliginea</b></i> inoculated. The plants are then placed in an incubation booth at about 20 ° C and 100% relative humidity.

009110 Days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

0092From the table below it is clear that the effect found of the active compound combinations according to the invention is greater than the calculated (see above), ie that a synergistic effect is present.<tables id="tabl0006" num="0006"><img file="EP1593307A2_D0095.tif" /></tables>

<b>Example F</b>

Botrytis test (bean) / protective

0093<dl id="dl0007"><dt>Solvent:</dt><dd>47 Parts by weight acetone</dd><dt>emulsifier:</dt><dd>3 Parts by weight of alkylaryl polyglycol ether</dd></dl>

0094To produce a suitable preparation of active compound, 1 part by weight of the active ingredient or of the active ingredient mixture with the specified amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration, or it dilutes a commercial formulation of active ingredient or drug combination with water to the desired concentration.

0095To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on each sheet 2 small<i><b>Botrytis cinerea</b></i> Overgrown Agarstückchen launched. The inoculated plants are placed in a darkened chamber at about 20 □ C and 100% relative humidity.

00962 Days after inoculation, the size of the infestation spots on the leaves is evaluated. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

0097From the table below it is clear that the effect found of the active compound combinations according to the invention is greater than the calculated (see above), ie that a synergistic effect is present.<tables id="tabl0007" num="0007"><img file="EP1593307A2_D0096.tif" /></tables>

<b>Example G</b>

Fusarium culmorum test (wheat) / seed treatment

0098The application of the active ingredients is carried out as a dry dressing. They are prepared by stripping the respective active ingredient with rock flour to a fine powdery mixture, which ensures a uniform distribution on the seed surface.

0099For pickling, shake the infected seed for 3 minutes with the mordant in a sealed glass bottle.

0100The wheat is sown with 2 x 100 grain 1 cm deep in a standard soil and cultivated in the greenhouse at a temperature of about 18 ° C and a relative humidity of about 95% in seed boxes, which are exposed daily 15 hours to light.

0101Approximately 3 weeks after sowing, the plants are evaluated for symptoms. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.<tables id="tabl0008" num="0008"><img file="EP1593307A2_D0097.tif" /></tables>

<b>Example H</b>

Puccinia test (wheat) / protective

0102<dl id="dl0008" compact="compact"><dt>Solvent:</dt><dd>25 Parts by weight of N, N-dimethylacetamide</dd><dt>emulsifier:</dt><dd>0.6 part by weight of alkylaryl polyglycol ether</dd></dl>

0103To produce a suitable preparation of active compound, 1 part by weight of active ingredient or combination of active ingredients with the specified amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration or dilutes a commercial formulation of active ingredient or drug combination with water to the desired concentration.

0104To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried, the plants are treated with a conidia suspension of<i><b>Puccinia recondita</b></i> sprayed. The plants remain for 48 hours at 20 ° C and 100% relative humidity in an incubation cabin.

0105The plants are then placed in a greenhouse at a temperature of about 20 ° C and a relative humidity of 80% to promote the development of rust pustules.

010610 Days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.<tables id="tabl0009" num="0009"><img file="EP1593307A2_D0098.tif" /></tables>