DE102006010204A1 - Drug combinations with insecticidal and acaricidal properties - Google Patents

Abstract

The new mixtures containing at least one active ingredient of the formula (I), $ F1 where Hal stands for chlorine, bromine or iodine, and at least one of the active ingredients 1 to 14 listed in the description from the class of insect growth regulators have very good insecticidal properties.

Description

The The present invention relates to novel drug combinations which from at least one known compound of formula (I) on the one hand and at least one other known active substance from the class of On the other hand, benzoylureas exist and are very good for controlling animal pests like insects and / or mites are suitable.

wobei
Hal für Chlor, Brom oder Iod steht,
* ein Kohlenstoffatom in der R- oder der S-Konfiguration, bevorzugt in der S-Konfiguration, kennzeichnet,
Insektizide Wirkung aufweisen. Dies gilt für die racemische Form der Verbindungen (EP-A 1 006 107) und in noch höherem Maß für die (S)-konfigurierten Enantiomere (unveröffentlichte japanische Patentanmeldung JP 2005-239974). Im Einzelnen seien die Verbindungen (Ia), (Ib) und (Ic) genannt.It is already known that compounds of the formula (I)

in which
Hal is chlorine, bromine or iodine,
* denotes a carbon atom in the R or S configuration, preferably in the S configuration,
Have insecticidal activity. This applies to the racemic form of the compounds (EP-A 1 006 107) and, to an even greater degree, to the (S) -configured enantiomers (unpublished Japanese patent application JP 2005-239974). Specifically, the compounds (Ia), (Ib) and (Ic) may be mentioned.

(Ia) :( S) -3-iodo-N ¹ - {2-methyl-4- [1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl} -N ² - (1-methyl phthalamide -2-methylsulphonylethyl)

• a) Benzoylharnstoffe wie 1. Chlorfluazuron (bekannt aus DE-A 28 18 830)
  
  2. Diflubenzuron (bekannt aus DE-A 21 23 236)
  
  3. Lufenuron (bekannt aus EP-A 0 179 022)
  
  4. Teflubenzuron (bekannt aus EP-A 0 052 833)
  
  5. Triflumuron (bekannt aus DE-A 26 01 780)
  
  6. Novaluron (bekannt aus US 4,980,376 )
  
  7. Hexaflumuron (bekannt aus EP-A 0 071 279)
  
  8. Bistrifluoron (DBI-3204) (bekannt aus WO 98/00394)
  
  9. Flufenoxuron (bekannt aus EP-A 0 161 019)
  
  10. Buprofezin (bekannt aus Proc. Br. Crop Prot. Conf. – Pests Dis., 1981, 1, 59)
  
• b) Chitin-Synthese-Inhibitoren wie 11. Cyromazine (bekannt aus GB-A 1 587 573)
  
• c) Juvenile Hormone Mimetika wie 12. Pyriproxifen
  
• d) Molting hormone Agonisten wie 13. Tebufenozide (bekannt aus US 4,985,461 )
  
  14. Methoxyfenozide (bekannt aus US 5,344,958 )
  

Furthermore, it is known that certain insect growth regulators have insecticidal activity. These include, for example:

• a) benzoylureas such as 1. chlorofluorurane (known from DE-A 28 18 830)
  
  2. Diflubenzuron (known from DE-A 21 23 236)
  
  3. Lufenuron (known from EP-A 0 179 022)
  
  4. Teflubenzuron (known from EP-A 0 052 833)
  
  5. Triflumuron (known from DE-A 26 01 780)
  
  6. Novaluron (known from US 4,980,376 )
  
  7. Hexaflumuron (known from EP-A 0 071 279)
  
  8. Bistrifluorone (DBI-3204) (known from WO 98/00394)
  
  9. Flufenoxuron (known from EP-A 0 161 019)
  
  10. Buprofezin (known from Proc. Br. Crop Prot. Conf. - Pests Dis., 1981, 1, 59)
  
• b) chitin synthesis inhibitors such as 11th cyromazine (known from GB-A 1 587 573)
  
• c) juvenile hormones mimetics like 12. Pyriproxifen
  
• d) Molting hormone agonists such as 13. Tebufenozide (known from US 4,985,461 )
  
  14. Methoxyfenozide (known from US 5,344,958 )
  

Surprisingly the insecticidal activity of the active ingredient combination according to the invention is essential higher than the sum of the effects of each agent. It is not predictable true synergistic effect before and not just one Addition of activities.

The active compound combinations according to the invention contain in addition to at least one active ingredient of formula (I) in enantiomerically pure Form or as a mixture of the two enantiomers in any ratio at least one of the above listed individually Insect growth regulators 1 to 14.

Prefers contain the active compound combinations according to the invention one of the active ingredients (Ia), (Ib) or (Ic) and one of the above individually listed Insect growth regulators 2, 3, 5, 6, or 9.

Especially preferred are the mixtures listed in Table 1.

Table 1

Very particular preference is given to the mixtures listed in Table 2. Table 2

If the active ingredients in the active compound combinations according to the invention in certain weight ratios are present, the synergistic effect is particularly evident.

however can the weight ratios the active ingredients in the drug combinations in a relatively large area be varied. In general, the combinations according to the invention contain an active ingredient of the formula (I) and one of the insect growth regulators 1 to 14 in the following preferred and particularly preferred Mixing ratios:

preferred Mixing ratio: 125: 1 to 1: 125 Especially preferred mixing ratio: 25: 1 until 1:25

The mixing ratios based on weight ratios. The relationship is to be understood as an active ingredient of the formula (I): insect growth regulator.

The active compound combinations according to the invention are suitable for good plant tolerance, favorable toxicity to warm-blooded animals and good environmental compatibility for the protection of plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and mollusks in agriculture, horticulture, livestock, forests, gardens and recreational facilities, in the protection of materials and materials and in the hygiene sector. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The above mentioned pests include:
From the order of the Anoplura (Phthiraptera) eg Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.

Out the class of arachnids e.g. Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.

Out the class of bivalva e.g. Dreissena spp.

Out the order of Chilopoda e.g. Geophilus spp., Scutigera spp.

Out the order of Coleoptera e.g. Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus; Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus Spp., Sphenophorus spp., Starchus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., xylotrechus spp., Zabrus spp.

Out the order of the collembola e.g. Onychiurus armatus.

Out the order of Dermaptera e.g. Forficula auricularia.

Out the order of the diplopoda e.g. Blaniulus guttulatus.

Out the order of the Diptera e.g. Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp. Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia spp., Tipula paludosa, Wohlfahrtia spp.

Out the class of Gastropoda e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.

From the class of helminths such as Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum Spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana , Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomes spp, Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.

Farther can be protozoa, such as Eimeria fight.

Out the order of the Heteroptera e.g. Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris Hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.

Out the order of Homoptera e.g. Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii.

Out the order of Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

Out the order of isopods e.g. Armadillidium vulgare, Oniscus asellus, Porcellio scaber.

Out the order of Isoptera e.g. Reticulitermes spp., Odontotermes spp.

Out the order of Lepidoptera e.g. Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp. Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella, Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema oryzae, Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, tinea pellionella, tineola bisselliella, tortrix viridana, Trichoplusia spp.

Out the order of Orthoptera e.g. Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.

Out the order of siphonaptera e.g. Ceratophyllus spp., Xenopsylla cheopis.

Out the order of Symphyla e.g. Scutigerella immaculata.

Out the order of Thysanoptera e.g. Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.

Out the order of Thysanura e.g. Lepisma saccharina.

To the plant parasite Nematodes belong e.g. Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipenetrans, Xiphinema spp.

The active compound combinations according to the invention are characterized in particular by strong effect against ...

The active compound combinations according to the invention can optionally in certain concentrations or application rates also as herbicides, safeners, growth regulators or agents for Improvement of plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including agents against viroids) or as an agent against MLO (Mycoplasma-like-organism) and RLO (Rickettsia-like-organism). They leave optionally also as intermediates or precursors for the synthesis use other active ingredients.

According to the invention, all Plants and parts of plants are treated. Among plants are here understood all plants and plant populations, as desired and undesirable Wild plants or crops (including naturally occurring crops). Crops can Be plants by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or Combinations of these methods can be obtained, including transgenic ones Plants and including protected by plant variety rights or non-protectable plant varieties. Under plant parts are all above ground and underground Parts and organs of plants, such as shoot, leaf, flower and root By way of example, leaves, needles, stems, stems, flowers, fruiting bodies, fruits and Seeds and roots, tubers and rhizomes are listed. Part of the plant parts also harvested material as well as vegetative and generative propagation material, For example, cuttings, tubers, rhizomes, offshoots and seeds.

The Treatment according to the invention the plants and plant parts are carried out with the active ingredient combinations directly or by acting on their environment, habitat or Storage room after the usual Treatment methods, e.g. by dipping, spraying, evaporating, misting, Spreading, spreading, injecting and propagating material, in particular in seed, still by single or multi-layer wrapping.

The Drug combinations can in the usual Formulations are transferred, like solutions, emulsions, Spray powder, water and oil based Suspensions, powders, dusts, Pastes, soluble Powder, soluble Granules, granules, suspension emulsion concentrates, drug-impregnated Natural products, drug-impregnated synthetic substances, fertilizers as well as finest encapsulations in polymeric materials.

These Formulations are prepared in a known manner, e.g. by Mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. The Preparation of the formulations is carried out either in suitable plants or even before or during the application.

When Excipients can find substances that are suitable to the agent itself or and / or preparations derived therefrom (for example spray liquor, seed dressing) to give special properties, such as certain technical properties and / or special biological properties. As typical Additives are suitable: extenders, solvents and carriers.

Suitable extenders are, for example, water, polar and non-polar organic chemical liquids, for example from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenes zolene, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, etherified and / or esterified), ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly) ethers, the simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulfones and sulfoxides (such as dimethyl sulfoxide).

in the Traps of using water as diluent may be e.g. also organic solvents as auxiliary solvent be used. As liquid solvent are essentially in question: aromatics, such as xylene, toluene, or Alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic Hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylsulfoxide, as well as water.

Suitable solid carriers are:
For example, ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals, such as finely divided silica, alumina and silicates, as solid carriers for granules in question: eg broken and fractionated natural rocks such Calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are nonionic and / or ionic substances, for example from the classes of alcohol POE and / or POP ethers, acid and / or POPPOE esters, alkylaryl and / or POP POE ethers, fatty and / or POP-POE adducts, POE and / or POP polyol derivatives, POE and / or POP sorbitol or sugar adducts, alkyl or aryl sulfates, sulfonates and phosphates or the corresponding PO-ether adducts. Further suitable oligo- or polymers, for example starting from vinylic monomers, from acrylic acid, from EO and / or PO alone or in combination with, for example, (poly) alcohols or (poly) amines. Ferer can find use lignin and its sulfonic acid derivatives, simple and modified celluloses, aromatic and / or aliphatic sulfonic acids and their adducts with formaldehyde.

It can in the formulations adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped Polymers such as gum arabic, polyvinyl alcohol, Polyvinyl acetate, as well as natural Phospholipids such as cephalins and lecithins and synthetic phospholipids.

It can Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and Metal phthalocyanine dyes and trace nutrients such as salts of iron, Manganese, boron, copper, cobalt, molybdenum and zinc are used.

Further Additives can Fragrances, mineral or vegetable optionally modified oils, waxes and nutrients (also trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc be.

Farther may be included Stabilizers such as cold stabilizers, Preservatives, antioxidants, light stabilizers or other chemical and / or physical stability improving agents.

The Formulations generally contain between 0.01 and 98% by weight Active ingredient, preferably between 0.5 and 90%.

The active compound combinations according to the invention can in commercial Formulations and in those prepared from these formulations Forms of use mixed with other active substances, such as insecticides, Attractants, sterilants, bactericides, acaricides, nematicides, Fungicides, growth regulators or herbicides. To the insecticides count For example, phosphoric acid esters, carbamates, Carbonsäureester, chlorinated hydrocarbons, phenylureas, by microorganisms Fabrics u.a.

Also a mixture with other known active substances, such as herbicides or with fertilizers and growth regulators is possible.

The active compound combinations according to the invention can also when used as insecticides in their commercial Formulations and in those prepared from these formulations Application forms in mixture with synergists are present. synergists are compounds that increase the effect of the active ingredients without the added synergist itself being active got to.

Of the Active substance content prepared from the commercial formulations Application forms can vary widely. The drug concentration of the application forms can be from 0.00000001 up to 95% by weight of active ingredient, preferably between 0.00001 and 1% by weight.

The Application is done in a custom forms adapted to the applications Wise.

As already mentioned above, can According to the invention, all plants and their parts are treated. In a preferred embodiment are wild or by conventional biological breeding methods, such as crossing or protoplast fusion obtained plant species and Treated plant varieties and their parts. In a further preferred embodiment are transgenic plants and plant varieties produced by genetic engineering Methods if necessary in combination with conventional methods were obtained (Genetically Modified Organisms) and their parts treated. The terms "parts" or "parts of plants" or "plant parts" have been explained above.

Especially plants according to the invention are preferred the respective commercial or plant varieties in use. Among plant varieties one understands plants with new characteristics ("Traits"), which by both conventional breeding, by mutagenesis or by recombinant DNA techniques are. This can Be varieties, biotypes and genotypes.

ever according to plant species or plant varieties, their location and growth conditions (Floors, Climate, vegetation period, nutrition) can by the treatment according to the invention also superadditives ("synergistic") effects occur. For example, reduced application rates and / or expansions of the Spectrum of action and / or an increase in the effect of the invention can be used Substances and agents, better plant growth, increased tolerance across from high or low temperatures, increased tolerance to dryness or against water or soil salt content, increased flowering efficiency, easier harvest, Acceleration of maturity, higher Crop yields, higher quality and / or higher Nutritional value of Harvested products, higher Shelf life and / or workability of the harvested products possible, beyond the actually expected Go beyond effects.

The preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits"). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms salt, increased flowering, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products , higher shelf life and / or workability of the harvested products. Further and particularly emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants to certain herbicidal active substances. Examples of transgenic plants are the important crops such as cereals (wheat, rice), corn, soybeans, potatoes, sugar beets, tomatoes, peas and other vegetables, cotton, tobacco, oilseed rape and fruit plants (with the fruits apples, pears, citrus fruits and Grapes), with special emphasis on maize, soya, potato, cotton, tobacco and oilseed rape. Traits which are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins which are formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CryIA (a) , CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their combinations) in the plants (hereinafter "Bt plants"). Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene). The genes which confer the desired properties ("traits") can also occur in combinations with one another in the transgenic plants. As examples of "Bt plants" maize varieties, cotton varieties, soybean varieties and potato varieties are mentioned, which are among the commercial designations YIELD GARD ^® (for example maize, cotton, soya beans), KnockOut ^® (for example maize), StarLink ^® (for example maize), Bollgard ^® (cotton), NuCOTN ^® (cotton) and NewLeaf ^® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties may be mentioned, under the trade names Roundup Ready ^® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link ^® (tolerance to phosphinotricin, for example oilseed rape), IMI ^® (tolerance against imidazolinone) and ^STS® (tolerance to sulfonylureas eg corn). Herbicide-resistant (conventionally bred for herbicide tolerance) plants also sold under the name Clear field ^® varieties (eg maize) are mentioned. Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.

The listed Plants can particularly advantageous with the active compound combinations according to the invention be treated. The specified in the drug combinations above Preferential ranges also apply to the treatment of these plants. Particularly emphasized is the Plant treatment with the active compound combinations specifically mentioned in the present text.

The active compound combinations according to the invention not only act against plant, hygiene and storage pests, but also in the veterinary sector against animal parasites (ecto- and endoparasites) such as ticks, leather ticks, mange mites, running mites, flies (stinging and licking), parasitic fly larvae, lice , Hair pieces, featherlings and fleas. These parasites include:
From the order of the Anoplurida eg Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

Out order of Mallophagida and submissions Amblycerina and Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton Spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.

Out of the order Diptera and the suborders Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota 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.

Out the order of the siphonapterida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

Out the order of the heteropterid e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.

Out the order of Blattarida e.g. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.

Out the subclass of Acari (Acarina) 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.

Out the order of Actinedida (Prostigmata) and Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia Spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

The active compound combinations according to the invention are also suitable for fighting of arthropods, farm animals, e.g. Bovine, Sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, Chicken, Turkeys, ducks, geese, Bees, other pets such as e.g. Dogs, cats, caged birds, aquarium fish and so-called experimental animals, e.g. Hamster, guinea pig, Rats and mice affected. By fighting These arthropods are said to be deaths and reductions in performance (in the case of meat, milk, wool, hides, eggs, Honey, etc.) are reduced, so that through the use of the active compound combinations according to the invention a more economical and easier animal husbandry is possible.

The Application of the active compound combinations according to the invention happens in the veterinary sector and in animal husbandry in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, Granules, pastes, boluses, the feed-through process, suppositories, by parenteral administration, as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), Implants, by nasal application, by dermal application in Form for example of diving or bathing (dipping), spraying (spray), infusing (Pour-on and spot-on), washing, powdering and with help of active substance-containing moldings, like collars, Ear tags, tail tags, limb bands, halters, marking devices etc.

at the application for Livestock, poultry, Pets etc. can be the drug combinations as formulations (For example, powders, emulsions, flowable agents) containing the active ingredients in an amount of 1 to 80 wt .-%, directly or after 100 up to 10 000-fold dilution apply or use as a chemical bath.

It was also found that the active compound combinations according to the invention show a high insecticidal activity against insects, the technical Destroy materials.

By way of example and preferably without limiting however, the following insects are mentioned:
Beetles such as Hylotrupes 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 such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;
Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus;
Bristle tails like Lepisma saccharina.

Under technical materials are non-living in the present context Materials, such as preferably plastics, adhesives, Glues, papers and cartons, leather, wood, woodworking products and paints.

The ready to use means optionally further insecticides and optionally also contain one or more fungicides.

Regarding potential additional Zumischpartner be on the above insecticides and fungicides directed.

at the same time can the active compound combinations according to the invention for protection against the growth of objects, in particular hulls, sieves, Nets, structures, wharves and signal systems connected with sea or brackish water are used.

Further can the active compound combinations according to the invention alone or in combination with other active ingredients as antifouling agent be used.

The active substance combinations are also suitable for controlling animal pests in household, hygiene and storage protection, in particular of insects, arachnids and mites, which are used in enclosed spaces, such as, for example, apartments, factory halls, offices, vehicle cabins and the like. occurrence. They can be used to control these pests, alone or in combination with other active ingredients and adjuvants in household insecticide products. They are effective against sensitive and resistant species and against all stages of development. These pests include:
From the order of Scorpionidea eg Buthus occitanus.

Out the order of Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutribicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.

Out the order of the Araneae e.g. Aviculariidae, Araneidae.

Out the order of opioids e.g. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.

Out the order of isopods e.g. Oniscus asellus, Porcellio scaber.

Out the order of the diplopoda e.g. Blaniulus guttulatus, Polydesmus spp.

Out the order of Chilopoda e.g. Geophilus spp.

Out the order of Zygentoma e.g. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.

Out the order of the Blattaria e.g. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

Out order of Saltatoria e.g. Acheta domesticus.

Out the order of Dermaptera e.g. Forficula auricularia.

Out the order of Isoptera e.g. Kalotermes spp., Reticulitermes spp.

Out the order of Psocoptera e.g. Lepinatus spp., Liposcelis spp.

Out the order of Coleoptera e.g. Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.

Out the order of the Diptera e.g. Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.

Out the order of Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.

Out the order of siphonaptera e.g. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.

Out the order of Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.

Out the order of the anoplura e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix, Phthirus pubis.

Out the order of the Heteroptera e.g. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

The Application in the field of household insecticides takes place alone or in combination with other suitable active substances, such as phosphoric esters, Carbamates, pyrethroids, neonicotinoids, growth regulators or agents from other known classes of insecticides.

The Application is in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, Fog machines, foggers, foams, Gels, evaporator products with evaporator plates made of cellulose or plastic, Liquid evaporators, Gel and membrane evaporators, propeller-driven evaporators, energy-free or passive evaporation systems, moth papers, moth bags and Moth gels, as granules or dusts, in straw baits or Bait stations.

The good insecticidal activity of the active compound combinations according to the invention is apparent from the examples below. While the individual active ingredients weaknesses in effect show the combinations have an effect over a simple effect summation goes beyond.

One synergistic effect is always present in active ingredients, though the effect of the drug combinations is greater than the sum of the effects the individually applied active ingredients.

The expected effect for a given combination of two drugs can be calculated according to SR Colby, Weeds 15 (1967), 20-22 as follows:
If
X means the degree of killing, expressed in% of the untreated control, when using the active ingredient A at a rate of mg / ha or in a concentration of m ppm,
Y means the degree of killing, expressed in% of the untreated control, when using the active substance B in an application rate of ng / ha or in a concentration of n ppm, and
E means the degree of killing, expressed in% of the untreated control, when using the active compounds A and B at application rates of m and ng / ha or in a concentration of m and n ppm,
then

is the actual kill rate greater than calculated, the combination is over-additive in its kill, i. it lies synergistic effect. In this case, the actually observed kill rate to be taller as the one from the above Formula calculated value for the expected kill rate (E).

Example A Phaedon cochleariae larval test Solvent: 7 parts by weight of dimethylformamide emulsifier: 2 parts by weight of alkylaryl polyglycol ether

to Preparation of a suitable preparation of active ingredient 1 part by weight of active compound is mixed with the stated amounts solvent and emulsifier and diluted concentrate with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped in the preparation of active compound of the desired concentration treated and with larvae of the horseradish leaf beetle (Phaedon cochleariae) occupied as long as the leaves are still wet.

To the desired Time will be the killing determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae killed were. The determined kill values billed according to the Colby formula (see sheet 1).

• * gef. = gefundene Wirkung
• ** ber. = nach der Colby-Formel berechnete Wirkung

Tabelle A Pflanzenschädigende Insekten Phaedon cochleariae Larven – Test

• * gef. = gefundene Wirkung
• ** ber. = nach der Colby-Formel berechnete Wirkung

Beispiel B Plutella xylostella – Test (sensibler Stamm) Lösungsmittel: 7 Gewichtsteile Dimethylformamid Emulgator: 2 Gewichtsteile Alkylarylpolyglykolether In this test, the following active ingredient combinations according to the present application showed a synergistically enhanced effectiveness in comparison to the individually applied active ingredients: (Ib) + Novaluron, (Ib) + Flufenoxuron, (Ib) + Lufenuron. Table A Plant Harmful Insects Phaedon cochleariae larvae test

• * gef. = found effect
• ** calc. = calculated according to the Colby formula

Table A Plant Harmful Insects Phaedon cochleariae larvae test

• * gef. = found effect
• ** calc. = calculated according to the Colby formula

Example B Plutella xylostella test (sensitive strain) Solvent: 7 parts by weight of dimethylformamide emulsifier: 2 parts by weight of alkylaryl polyglycol ether

to Preparation of a suitable preparation of active ingredient 1 part by weight of active compound is mixed with the stated amounts solvent and emulsifier and diluted concentrate with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped in the preparation of active compound of the desired concentration treated with caterpillars of the cabbage moth (Plutella xylostella), as long as the leaves are still wet.

To the desired Time will be the killing determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed. The determined kill rates billed according to the Colby formula (see sheet 1).

• * gef. = gefundene Wirkung
• ** ber. = nach der Colby-Formel berechnete Wirkung

Beispiel C Plutella xylostella – Test (resistenter Stamm) Lösungsmittel: 7 Gewichtsteile Dimethylformamid Emulgator: 2 Gewichtsteile Alkylarylpolyglykolether In this test, the following active ingredient combinations according to the present application showed a synergistically enhanced effectiveness compared to the individual active ingredients: (Ib) + Flufenoxuron Table B Plant-damaging insects Plutella xylostella test (sensitive strain)

• * gef. = found effect
• ** calc. = calculated according to the Colby formula

Example C Plutella xylostella test (resistant strain) Solvent: 7 parts by weight of dimethylformamide emulsifier: 2 parts by weight of alkylaryl polyglycol ether

to Preparation of a suitable preparation of active ingredient 1 part by weight of active compound is mixed with the stated amounts solvent and emulsifier and diluted concentrate with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped in the preparation of active compound of the desired concentration treated with caterpillars of the cabbage moth (Plutella xylostella), as long as the leaves are still wet.

To the desired Time will be the killing determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed. The determined kill rates billed according to the Colby formula (see sheet 1).

• * gef. = gefundene Wirkung
• ** ber. = nach der Colby-Formel berechnete Wirkung

Beispiel D Spodoptera frugiperda – Test Lösungsmittel: 7 Gewichtsteile Dimethylformamid Emulgator: 2 Gewichtsteile Alkylarylpolyglykolether In this test, the following active ingredient combinations according to the present application showed a synergistically enhanced efficacy compared to the individual active ingredients used: (Ib) + flufenoxuron, (Ib) + triflumuron Table C Plant-damaging insects Plutella xylostella - test (resistant strain)

• * gef. = found effect
• ** calc. = calculated according to the Colby formula

Example D Spodoptera frugiperda test Solvent: 7 parts by weight of dimethylformamide emulsifier: 2 parts by weight of alkylaryl polyglycol ether

to Preparation of a suitable preparation of active ingredient 1 part by weight of active compound is mixed with the stated amounts solvent and emulsifier and diluted concentrate with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped in the preparation of active compound of the desired concentration treated and occupied with caterpillars of the armyworm (Spodoptera frugiperda), while the leaves are still are wet.

To the desired Time will be the killing determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed. The determined kill rates billed according to the Colby formula (see sheet 1).

• * gef. = gefundene Wirkung
• ** ber. = nach der Colby-Formel berechnete Wirkung

In this test, the following active ingredient combination according to the present application showed a synergistically enhanced effectiveness in comparison to the individually applied active ingredients: (Ib) + Methoxyfenozide Table D Plant damaging insects Spodoptera frugiperda test

• * gef. = found effect
• ** calc. = calculated according to the Colby formula

Claims (10)

Composition comprising a mixture (a) of at least one active substance of the formula (I)

wherein Hal represents chlorine, bromine or iodine, * denotes a carbon atom in the R or S configuration, and (b) at least one of the following active ingredients: chlorofluoroburon diflubenzuron lufenuron teflubenzuron triflumuron novaluron hexaflumuron bistrifluorone flufenoxuron buprofezin cyromazine pyriproxifen tebufenozide methoxyfenozide Means according to claim 1 containing at least one of the following active ingredients diflubenzuron lufenuron triflumuron novaluron flufenoxuron Methoxyfenozid Composition according to claim 1 containing one of the following active substance combinations

Use of agents as in claims 1 to 3 defined, to combat animal pests. Use of agents as in claims 1 to 3 defines, for the treatment of seeds. Use of agents as in claims 1 to 3, for the treatment of transgenic plants. Use of agents as in claims 1 to 3, for treating seed of transgenic plants. Seed which is treated with an agent as in claims 1 to 3 defined, was treated. Method of control of unwanted animal pests, characterized in that means as in claims 1 to 3 defines, on the unwanted animal pests and / or their habitat and / or seed. Process for the preparation of insecticidal agents, characterized in that mixtures as in claims 1 to 3, mixed with extenders and / or surfactants.