EP1855532A2 - Active ingredient combinations having insecticide and acaricide properties - Google Patents

Abstract

The invention relates to novel active ingredient combinations of defined cyclic ketoenols and ethiprols, said active ingredient combinations having very good insecticide and acaricide properties.

Description

Drug combinations with insecticides and acaricidal properties

The present invention relates to novel drug combinations which consist of known cyclic ketoenols on the one hand and ethiproles on the other hand and are very suitable for controlling animal pests such as insects and unwanted acarids.

It is already known that certain cyclic ketoenols possess herbicidal, insecticidal and acaricidal properties. The effectiveness of these substances is good, but leaves at low application rates in some cases to be desired.

Unsubstituted, bicyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-355 599 and EP-A-415 211) and substituted monocyclic 3-arylpyrrolidine are known to have herbicidal, insecticidal or acaricidal activity 2,4-dione derivatives (EP-A-377 893 and EP-A-442 077).

Also known are polycyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-442 073) and 1H-arylpyrrolidine-dione derivatives (EP-A-456 063, EP-A-521 334, EP-A- 596 298, EP-A-613 884, EP-A-613 885, WO 94/01 997, WO 95/26 954, WO 95/20572, EP-A-0 668 267,

WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02243, WO 97/36 868, WO 97/43 275, WO 98/05 638, WO 98/06 721, WO 98 / 25 928, WO 99/16748, WO 99/24 437, WO 99/43 649, WO 99/48 869, WO 99/55 673, WO 01/17972, WO 01/23354, WO 01/74770, WO 04 / 007448, WO 04/024688, WO 04/065366, WO 04/080962).

It has now been found that compounds of the formula (I)

in which

X is halogen, alkyl, alkoxy, haloalkyl, haloalkoxy or cyano,

W, Y and Z independently of one another represent hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy or cyano, -

A is hydrogen, in each case optionally halogen-substituted alkyl, alkoxyalkyl, saturated, optionally substituted cycloalkyl in which optionally at least one ring atom is replaced by a heteroatom,

B is hydrogen or alkyl,

A and B, together with the carbon atom to which they are attached, represent a saturated or unsaturated unsubstituted or substituted cycle, optionally containing at least one heteroatom,

D is hydrogen or an optionally substituted radical from the group consisting of alkyl, alkenyl, alkoxyalkyl, saturated cycloalkyl, in which optionally one or more ring members are replaced by heteroatoms,

A and D together with the atoms to which they are bonded represent a saturated or unsaturated and optionally at least one heteroatom-containing, unsubstituted or substituted in the A ₅ D part of the cycle,

G is hydrogen (a) or one of the groups

o _L R ⁴

^ R ¹ (b), ^ M ^'R2 (C). / ^SO ^ - ^R3 «0, / ^ (β),

stands,

wherein

E is a metal ion or an ammonium ion,

L is oxygen or sulfur,

M is oxygen or sulfur,

R! in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionally substituted by halogen, alkyl or alkoxy-substituted cycloalkyl which is replaced by at least - -

a heteroatom may be interrupted, in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,

R is in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or in each case optionally substituted cycloalkyl, phenyl or benzyl,

R ^{3 is} optionally halogen-substituted alkyl or optionally substituted phenyl,

4 5

R and R independently of one another are in each case optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio or in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio and

6 7

R and R independently of one another represent hydrogen, in each case optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, optionally substituted phenyl, optionally substituted benzyl or together with the N-atom to which they are attached, optionally substituted by Oxygen or sulfur interrupted optionally substituted ring and

ethiprole

known from DE-A-19653417 possess very good insecticidal and acaricidal properties.

Surprisingly, the insecticidal and acaricidal activity of the active compound combinations according to the invention is substantially higher than the sum of the effects of the individual active substances. There is an unpredictable true synergistic effect and not just an effect supplement.

Preference is given to active compound combinations comprising compounds of the formula (I) in which the radicals have the following meaning:

W preferably represents hydrogen, C _j -C ₄ alkyl Cj-C ₄ -alkoxy, chlorine, bromine or fluorine,

X preferably represents C _j ^ -C alkyl, C ₁ -C ₄ -alkoxy, C _j -C ₄ haloalkyl, fluorine, chlorine or bromine,

Y and Z independently of one another preferably represent hydrogen, Cj-C ₄ -alkyl, halogen, C ₁ -C ₄ -alkoxy or Cj-C ₄ haloalkyl,

A preferably represents hydrogen or respectively optionally sub- stituiertes by halogen C _r C ₆ alkyl or C3-C8-cycloalkyl,

B is preferably hydrogen, methyl or ethyl,

A, B and the carbon atom to which they are attached are preferably saturated C ₃ -C ₆ -cycloalkyl, in which optionally one ring member is replaced by oxygen or sulfur and which is optionally mono- or disubstituted by C ₁ -C ₄ -alkyl, trifluoromethyl or C ₁ -C ₄ -alkoxy is substituted,

D is preferably hydrogen, in each case optionally fluorine- or chlorine-substituted C ₁ -C ₆ -alkyl, C ₃ -C ₄ -alkenyl or C ₃ -C ₆ -cycloalkyl,

A and D together preferably represent optionally methyl-substituted C ₃ -C ₄ -alkanediyl, in which optionally a methylene group is replaced by sulfur _.

G is preferably hydrogen (a) or one of the groups

^ R ¹ (b), Λ _M ' ^{R2 (C)} . / ^SO ^ - ^R3 Often -J ^ _(e) ,

R °

E ® or /? NN _\ ? (g) in particular for (a), (b), (c) or (g)

in which

E is a metal ion or an ammonium ion,

L stands for oxygen or sulfur and

M is oxygen or sulfur,

R ¹ preferably represents in each case optionally halogen-substituted Gj-Cio-alkyl, C ₂ -C ₁₀ -alkenyl, C _r C _{4 alkylthio-Ci-C4-alkyl} or optionally substituted by fluorine, chlorine, _Cj-C4 alkyl or Cj-C _Σ -alkoxy-substituted C ₃ -C ₆ ~ cycloalkyl,

optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C _r C ₄ alkyl C ₁ -C ₄ alkoxy, trifluoromethyl or trifluoromethoxy-substituted phenyl,

each optionally substituted by chlorine or methyl substituted pyridyl or thienyl,

R ² preferably represents in each case optionally fluorine- or chlorine-substituted C 1 -

Cjo alkyl, C ₂ ~ Cio-alkenyl, C _r C ₄ alkoxy-C _r C ₄ alkyl,

for optionally substituted by methyl or methoxy C ₅ -C ₆ -cycloalkyl or

in each case optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C _r C ₄ alkyl, Cj-C ₄ alkoxy, trifluoromethyl or TrifluormeÜioxy substituted phenyl or benzyl,

R ³ preferably represents optionally fluorine-substituted C 1 -C ₄ -alkyl or represents optionally by fluorine, chlorine, bromine, C ₃ -C ₄ alkoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro substituted phenyl, R ⁴ preferably represents in each case optionally fluorine- or chlorine-substituted Ci-. C ₄ -Allcyl, C] -C ₄ -alkoxy ₃ QQ-alkylamino, C] -C ₄ -alkylthio or represents in each case optionally fluorine-, chlorine, bromine, nitro, cyano, QQ-alkoxy, trifluoromethoxy, Ci-C ₄ - alkylthio, C _r C ₄ haloalkylthio, C _r C ₄ alkyl or trifluoromethyl-substituted phenyl, phenoxy or phenylthio,

R ⁵ is preferably C ₁ -C ₄ -alkoxy or C _r C ₄ thioalkyl,

R ⁶ preferably represents C _r C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C _r C ₆ alkoxy, C ₃ -C ₆ alkenyl, C ₁ -C ₄ -alkoxy-Ci-C ₄ -BIlCyI,

R ⁷ preferably represents C _r C ₆ alkyl, C ₃ -C ₆ alkenyl or alkyl C _r C ₄ alkoxy-C _r C _4,

R ⁶ and R ⁷ together preferably represent an optionally substituted by methyl or ethyl C ₃ -C ₆ alkylene, in which optionally a carbon atom is replaced by oxygen or sulfur.

W. is particularly preferably hydrogen, methyl, ethyl, chlorine, bromine or methoxy,

X particularly preferably represents chlorine, bromine, methyl, ethyl, propyl, i-propyl,

Methoxy, ethoxy or trifluoromethyl,

Y and Z are more preferably independently of one another hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, trifluoromethyl or methoxy,

A particularly preferably represents methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclopentyl or cyclohexyl,

B is particularly preferably hydrogen, methyl or ethyl,

A, B and the carbon atom to which they are attached are particularly preferably saturated Cβ-cycloalkyl, in which optionally a ring member is replaced by oxygen and which is optionally substituted by methyl, ethyl, methoxy, ethoxy, propoxy or butoxy,

D is particularly preferably hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, AlyI, cyclopropyl, cyclopentyl or cyclohexyl, _ _

A and D together are particularly preferably C ₃ -C ₄ -alkanediyl optionally substituted by methyl,

G is particularly preferably hydrogen (a) or one of the groups

in which

M is oxygen or sulfur,

R ¹ particularly preferably represents C _r C ₈ alkyl, C ₂ -C ₄ alkenyl, methoxymethyl, ethoxymethyl, ethylthiomethyl, cyclopropyl, cyclopentyl or cyclohexyl,

optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, trifluoromethyl or trifluoromethoxy phenyl,

each optionally substituted by chlorine or methyl substituted pyridyl or thienyl,

R ² particularly preferably represents C ₁ -C ₆ -alkyl, C ₂ -C ₄ -alkenyl, methoxyethyl, etioxyethyl or phenyl or benzyl,

R ⁶ and R ⁷ independently of one another particularly preferably represent methyl, ethyl or together represent a C ₅ -alkylene radical in which the C ₃ -methylene group is replaced by oxygen.

W is very particularly preferably hydrogen or methyl,

X very particularly preferably represents chlorine, bromine or methyl,

Y and Z very particularly preferably independently of one another represent hydrogen, chlorine,

Bromine or methyl,

A, B and the carbon atom to which they are attached very particularly preferably represent saturated C ₆ -cycloalkyl in which optionally one ring member is replaced by oxygen and which is optionally monosubstituted by methyl, methoxy, ethoxy, propoxy or butoxy, D is very particularly preferably hydrogen,

G is very particularly preferably hydrogen (a) or one of the groups

®

in which

M is oxygen or sulfur,

R ¹ very particularly preferably represents C ₁ -C 8 -alkyl, C ₂ -C ₄ -alkenyl, methoxy-ethyl, ethoxymethyl, ethylmethylthio, cyclopropyl, cyclopentyl, cyclohexyl or

optionally substituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro phenyl,

each optionally substituted by chlorine or methyl pyridyl or

thienyl,

R ² is very particularly preferably represents C _r C ₈ alkyl, C ₂ -C ₄ -alkenyl, methoxyethyl, ethoxyethyl, phenyl or benzyl,

R ⁶ and R ⁷ independently of one another very particularly preferably represent methyl, ethyl or together represent a C ₅ -alkylene radical in which the C ₃ -methylene group passes through

Oxygen is replaced.

Particularly preferred are combinations of active substances containing compounds of the formula (I)

- -

and ethiprole.

The active ingredient combinations may also contain other fungicidal, acaricidal or insecticidal Zumischkomponenten beyond.

If the active ingredients in the active compound combinations according to the invention are present in certain weight ratios, the synergistic effect is particularly pronounced. However, the weight ratios of the drugs in the drug combinations can be varied in a relatively wide range. In general, the combinations according to the invention contain active compounds of the formula (I) and ethiproles in the following preferred and particularly preferred mixing ratios:

Preferred mixing ratio: 50: 1 to 1:50 _ _

Particularly preferred mixing ratio: 25: 1 to 1:25

The mixing ratios are based on weight ratios. The ratio is to be understood as the active ingredient of the formula (I): ethiprole.

The active compound combinations according to the invention are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which occur in agriculture, animal health, in forests, in the supply and protection of materials 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:

From the order of isopods e.g. Oniscus asellus, Armadillidium vulgaris, Porcellio scaber.

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

From the order of Chilopoda e.g. Geophilus carpophagus, Scutigera spp ..

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

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

From the order of Collembola e.g. Onychiurus armatus.

From the order of Orthoptera e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.

From the order of the Blattaria e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica.

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

From the order of Isoptera e.g. Reticulitermes spp ..

From the order of Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.

From the order of Thysanoptera eg Hercinothrips femoralis, Thrips tabaci, Thrips pahni, Frankliniella accidentalis. From the order of Heteroptera eg Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius,

Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, 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, Cnaphalocerus spp., Oulema oryzae.

From the order of Coleoptera e.g. 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, Anthonorus spp.,

Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis,

Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethses aeneus, Ptinus spp., Niptus hololeucus, Gibbia psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,

Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.

From the order of Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomoriunx pharaonis, Vespa spp.

From the order of Diptera eg Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora eryihrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp , Stomoxys spp., Oestrus spp., Hypoderma spp., Taban's spp., Tannia spp., Bibio hortulanus, Oscinella firit, Phorbia spp., Pegomyia hyoscyami, Cerititis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp.

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

From the class of arachnids, e.g. Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoropts spp , Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp.

The plant parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis,

Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.

The active substance combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble

Powders, granules, suspension-emulsion concentrates, active substance-impregnated natural and synthetic substances as well as finest encapsulation in polymeric substances.

These formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents.

In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes,

Chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example 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 dimethylformamide and dimethyl sulfoxide , as well as water. Suitable solid carriers are:

e.g. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates, as solid carriers for granules are suitable: e.g. broken 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 emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers. e.g.

Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

It can be used in the formulations adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers, such as

Gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives may be mineral and vegetable oils.

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.

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

The active compound combinations according to the invention can be present in commercially available formulations as well as in the formulations prepared from these formulations in admixture with other active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas

Microorganisms produced substances among other things 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 may also be present when used as insecticides in their commercial formulations as well as in the formulations prepared from these formulations in admixture with synergists. Synergists are

Compounds by which the effect of the active ingredients is increased without the added synergist itself must be active.

The active substance content of the application forms prepared from the commercial formulations can vary within wide ranges. The active ingredient concentration of the use forms may be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.

The application is done in a custom forms adapted to the application.

When used against hygiene and storage pests, the active substance combinations are distinguished by an excellent residual action on wood and clay and by a good alkali stability on limed substrates.

The active ingredient combinations according to the invention not only act against plant, hygiene and storage pests, but also on the veterinary sector against animal parasites (ectoparasites) such as ticks, leather ticks, mange mites, running mites, flies (stinging and licking), parasitizing fly larvae, lice, hair pieces. Featherlings and fleas. These parasites include:

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

From the order of Mallophagida and suborders Amblycerina and Ischnocerina, for example. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damaiina spp., Trichodectes spp., Felicola spp.

From the order Diptera and the suborders Nematocerina and Brachycerina eg 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., Hypodeπna spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of siphonapterida e.g. Pulex spp., Ctencephalides spp., Xenopsylla spp., Ceratophyllus spp.

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

Panstrongylus spp ..

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

From the subclass of Acaria (Acarida) and the orders of Meta and Mesostigmata e.g. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp ., Sternostoma spp., Varroa spp.

From the order of 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., Rnemidocoptes spp , Cytodites spp., Laminosioptes spp.

The active compound combinations according to the invention are also suitable for controlling arthropods which are farm animals, such as e.g. Cattle, Sheep, Goats, Horses,

Pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, caged birds, aquarium fish and so-called experimental animals, such. Hamsters, guinea pigs, rats and mice. By controlling these arthropods deaths and reductions in performance (in meat, milk, wool, hides, eggs, honey, etc.) are reduced so that a more economical and easier animal husbandry is possible through the use of the active ingredient combination of the invention.

The application of the active ingredient combination according to the invention takes place in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boilies, the feed-through

Method of suppositories, by parenteral administration, such as by - -

Injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal application in the form of, for example, dipping or bathing (dipping), spraying, pouring and spot-on, washing , the powdering and with the help of active substance-containing moldings, such as collars, ear tags, tail marks, limb bands, holsters, marking devices, etc.

When used for livestock, poultry, pets, etc., the active ingredient combinations may be used as formulations (for example, powders, emulsions, flowables) containing the active ingredients in an amount of 1 to 80% by weight, directly or after 100 to 10,000 dilution or use as a chemical bath.

In 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

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovülosum, 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

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

Termites like

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticuliteπnes flavipes,

Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.

Bristle tails like Lepisma saccharina. Technical materials in the present context are non-living materials, such as preferably plastics, adhesives, glues, papers and cardboard, leather, wood, wood processing products and paints.

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

By 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:

Lumber, 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 generally used in construction

Building or in the joinery use find.

The Wirkstoffkombinatjonen can be used as such, in the form of concentrates or commonly used formulations such as powder, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, e.g. 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 further processing aids.

The insecticides used for the protection of wood and wood-based materials means or

Concentrates contain the active ingredient according to the invention in a concentration of 0.0001 to 95 wt .-%, in particular 0.001 to 60 wt .-%.

The 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.

The solvent and / or diluent used is an organic-chemical solvent or solvent mixture and / or an oily or oily heavy-volatile organic-chemical solvent or solvent mixture and / or a polar organic solvent. chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agent.

As organic-chemical solvents are preferably oily or oily solvents having an evaporation number above 35 and a flash point above 30 ⁰ 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.

Mineral oils having a boiling range of 170 to 220 ⁰ C, white spirit having a boiling range of 170 to 22O ⁰ C, spindle oil with a boiling range of 250 to

350 ⁰ C, kerosene or aromatics boiling range of 160 to 280 ⁰ C, turpentine oil and the like are used.

In a preferred embodiment, liquid aliphatic hydrocarbons having a boiling range of 180 to 210 ⁰ C or high-boiling mixtures of aromatic and aliphatic hydrocarbons having a boiling range of 180 to 220 ⁰ C and / or

Lock oil and / or monochloronaphthalene, preferably α-monochloronaphthalene.

The organic low volatile oily or oily solvents having an evaporation number above 35 and a flash point above 30 ⁰ C, preferably above 45 ° C, can be partially replaced by light or medium volatile organic chemical solvents, with the proviso that the solvent mixture is also a

Evaporation number above 35 and a flash point above 30 ⁰ C, preferably above 45 ° C, and that the mixture is soluble or emulsifiable in this solvent mixture.

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

As organic-chemical binders in the context of the present invention, the known water-dilutable and / or in the organic-chemical

Solvents soluble or dispersible or emulsifiable synthetic resins and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-cumarone resin, silicone resin, drying vegetable and / or drying Oils and / or physically drying binders based on a

Natural and / or synthetic resin used.

The 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 per se known

Corrosion inhibitors and the like. Be used.

According 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.

The 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 failure. Preferably, they replace 0.01 to 30% of the binder (based on 100% of the binder used).

The 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.

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

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

Particularly effective wood protection is provided by large scale impregnation methods, e.g. Vacuum, double vacuum or printing process achieved.

At the same time, the active compound combinations according to the invention can be used for protection against growth of objects, in particular hulls, sieves, nets, structures, quaysides and signal systems, which come into contact with seawater or brackish water.

The growth of sessile oligochaetes, such as limeworm worms, shells and species of the group Ledamorpha (barnacles), such as various Lepas and scalpelum species, or species of the group Balanomorpha (barnacles), such as Baianus or Pollicipes species, increases the frictional resistance of As a result of increased energy consumption and, moreover, frequent drydocking periods, the operating costs are significantly increased.

In addition to the vegetation by algae, for example Ectocarpus sp. and Ceramium sp., is particularly the fouling by sessile Entomostraken groups, which are summarized under the name Cirripedia (cirripeds), particular importance.

It has now surprisingly been found that the erfindtmgsgemäßen active compound combinations have an excellent antifouling (anti-fouling) - effect.

By use of the active ingredient combination according to the invention, the use of heavy metals, such as e.g. in bis (trialkyltin) sulfides, tri-w-butyl tin laurate, tri-w-butyltin chloride, copper (I) oxide, triethyltin chloride, tri-n-butyl (2-phenyl-4-chlorophenoxy) -tin, tributyltin oxide, Molybdenum disulfide, antimony oxide, polymeric butyl titanate, phenyl (bispyridine) bismuth chloride, tri-buryltin fluoride, manganese ethylene bis-thiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc and copper salts of 2-pyridinethiol-1-oxide, bisdimethyldithiocarbamoylzinc ethylene bisthiocarbamate, zinc oxide, copper ( I) - ethylene bisdithiocarbamate, copper thiocyanate, copper naphthenate and Triburylzinn- halides are omitted or the concentration of these compounds are significantly reduced.

The ready-to-use antifouling paints may optionally contain other active substances, preferably algicides, fungicides, herbicides, molluscicides or other antifouling active ingredients. Suitable combination partners for the antifouling agents according to the invention are preferably:

Algicides like

2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophene, diuron, endothal, fentin acetate, isoproturon, methabenzothiazuron, oxyfluorfen, quinoclamine and

terbutryn;

Fungicides like

Benzo [έ] thiophenecarboxylic cyclohexylamide S, S-dioxide, dichlofluanid, fluoro-folpet, 3-iodo-2-propynyl-butylcarbamate, tolylfluanid and Azple as

Azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and tebuconazole;

Molluscicides like

Fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb;

or conventional antifouling agents such as

4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulfone, 2- (N, N-dimethyltbio-carbamoylthio) -5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridine - thiol-1-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4,6 - trichlorophenylmaleimide.

The antifouling agents used contain the active compound combinations according to the invention in a concentration of 0.001 to 50% by weight, in particular of 0.01 to 20

Wt .-%.

The antifouling agents of the invention further contain the usual ingredients, e.g. in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

Antifouling paints contain, in addition to the algicidal, fungicidal, molluscicidal and insecticidal insecticides according to the invention, in particular binders. Examples of approved binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, in particular in an aqueous system, vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / Acrymitrile rubbers, drying oils, such as linseed oil, rosin esters or modified hard resins in combination with tar or bitumen, asphalt and epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.

Optionally, paints also contain inorganic pigments, organic pigments or dyes which are preferably insoluble in seawater. Furthermore, can

Coating materials such as rosin are included to allow controlled release of the active ingredients. The paints may further contain plasticizers, rheology modifiers, and other conventional ingredients. Also in self-polishing antifouling systems, the compounds of the invention or the above-mentioned mixtures can be incorporated.

The active compound combinations are also suitable for controlling animal pests, in particular 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 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 e.g. Buthus occitanus.

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

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

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

From the order of the Isopoda eg Oniscus asellus, Porcellio scaber. ₃

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

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

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

From the order of the Blattaria e.g. Blatta orientalis, Blattella germanica, Blattella asahinai,

Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta miginosa, Supella longipalpa.

From the order of Saltatoria e.g. Acheta domesticus.

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

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

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

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

From the order of 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.

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

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

From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum. From the order of Anoplura eg Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis.

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

Application is in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, fog machines, foggers, foams, gels, evaporator products with cellulose or plastic evaporator plates, liquid evaporators, gel and membrane evaporators, propeller driven evaporators, energyless or passive evaporation systems, moth papers, moth cakes and moth gels, as granules or dusts, in litter or bait stations.

Erfϊndungsgemäß all plants and parts of plants can be treated. In this context, plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant breeders' rights. Plant parts are to be understood as meaning all aboveground and underground parts and organs of the plants, such as shoot, leaf, flower and root, examples being leaves, needles, stems, stems, flowers,

Fruits, fruits and seeds and roots, tubers and rhizomes are listed. The plant parts also include crop and vegetative and generative Vermelirungsmaterial, such as cuttings, tubers, Rhiozome, offshoots and seeds.

The treatment according to the invention of the plants and plant parts with the active substance combinations is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, spreading, spreading and in propagation material, in particular in seeds, further by single or multi-layer wrapping.

As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, wild species or plant species obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and plant varieties and their parts are treated. In another preferred embodiment, transgenic plants and plant varieties which have been obtained by genetic engineering, optionally in combination with conventional methods (Genetically Modified Organisms) and their parts treated. The term "parts" or "parts of plants" or "plant parts" has been explained above.

According to the invention, particular preference is given to plants of the respective commercial or in

Treated plant varieties.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also give rise to superadditive ("synergistic") effects. Thus, for example, reduced application rates and / or extensions of the activity spectrum and / or a

Enhancement of the efficacy of the materials and agents to be used, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salinity, increased flowering efficiency, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher storage capacity and / or machinability of the harvested products possible, which go beyond the actual expected 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 against certain herbicidal active substances. Examples of transgenic plants include the important crops such as cereals (wheat, rice), corn, soy, potato, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soy, potato, cotton and rapeseed should be highlighted. As properties ("Traits") are particularly emphasized the increased - -

Repelling the plants against insects by toxins produced in the plants, in particular those produced by the genetic material from Bacillus thuringiensis (eg by the genes CryΙA (a), CryΙA (b), CryΙA (c), CryUA, CrylHA, CrylHB2, Cry9c Cry2Ab, Cry3Bb and CryH ⁷ and their combinations) in the plants (hereinafter "Bt plants"). Traits that are also particularly emphasized are the increased tolerance of the plants to certain herbicidal 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. Examples of "Bt plants" are maize varieties, cotton varieties, soybean varieties and potato varieties that are marketed under the trade names YIELD GARD® (eg corn, cotton, soya), KnockOut® (eg corn), StarLink® (eg maize), Bollgard®. (Cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties, which are sold under the trade names Roundup Ready® (tolerance to

Glyphos, e.g. Corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, e.g., rapeseed), IMI® (tolerance to imidazolinone), and STS® (tolerance to sulfonylureas, e.g., corn). Herbicide-resistant plants (conventionally grown for herbicide tolerance) also include the varieties sold under the name Clearfeld® (for example corn). Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.

The listed plants can be treated particularly advantageously according to the invention with the Wirkstoffinischung invention. The preferred ranges given for the mixtures above also apply to the treatment of these plants. Particularly emphasized is the plant treatment with the mixtures specifically mentioned in the present text.

The good insecticidal and acaricidal activity of the active compound combinations according to the invention is evident from the examples below. While the individual active ingredients have weaknesses in effect, the combinations show an effect that goes beyond a simple action summation.

A synergistic effect is always present in insecticides and acaricides whenever the effect of the active ingredient combinations is greater than the sum of the effects of 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 substance A at a rate of m g / ha or in a concentration of m ppm,

Y means the degree of killing, expressed in% of the untreated control, when using the active ingredient B in an application rate of n g / 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 in an amount by weight of m and n g / ha or in a concentration of m and n ppm,

then

XYE = X ₊ Y- - ^ -

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

Example A

Myzus persicae test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight is mixed

Active ingredient with the specified amount of solvent and emulsifier and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) that are heavily infested with the peach aphid (Myzus persicae) are treated by being dipped into the preparation of active compound of the desired concentration.

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

In this test, z. For example, the following compounds of Preparation Examples have superior efficacy over the prior art:

Table A

Plant damaging insects

Myzus persicae - test

Active substance concentration killing in ppm in% after 6 ^d

Example (1-4) known

4 75

Ethiprole known

20 10

Example (1-4) + Ethiprole (1: 5) according to the invention obs. * Cal. ** 4 + 20 95 77.5

* obs. = observed effectiveness

** cal. = effectiveness calculated with Colby formula

Example B

Plutella Test

Solvent: 7 parts by weight dimethylfibramide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight is mixed

Active ingredient with the specified amount of solvent and emulsifier and the concentrate is diluted with emulsifier-containing water to the desired concentration.

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

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

In this test, z. For example, the following compounds of Preparation Examples have superior efficacy over the prior art:

- -

Table B

Plant damaging insects

Plutella xylostella - test

Active substance concentration killing in ppm in% after 6 ^d

Example (1-4) known

65

Ethiprole known

0.16

Example (1-4) + Ethiprole (25: 1) according to the invention obs. * Cal. **

4 + 0,16 75 65

obs. = observed efficacy

** cal. = effectiveness calculated with Colby formula

Example C

Boundary Concentration Test / Soil Insects - Treatment of transgenic plants

Test insect: Diabrotica balteata - larvae in soil

Solvent: 7 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The preparation of active compound is poured onto the ground. Here, the concentration of the active ingredient in the preparation plays virtually no role, the only decisive factor is the

Weight of active ingredient per unit volume of soil, which is expressed in ppm (mg / l). The soil is poured into 0.25 1 pots and allowed to stand at 20 ⁰ C.

Immediately after the start, 5 pre-germinated corn kernels of the YIELD GUAKD variety (trademark of Monsanto Comp., USA) are placed per pot. After 2 days the appropriate test insects are placed in the treated soil. After a further 7 days, the effectiveness of the active ingredient is determined by counting the accumulated maize plants (1 plant = 20% effect).

Example D

Heliothis virescens - test - treatment of transgenic plants

Solvent: 7 parts by weight of acetone

Emulsifier: 1 part by weight of alkylarylpolyglycol either

To prepare a suitable preparation of active compound, 1 part by weight is mixed

Active substance with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Soybean shoots (Glycine max) of the variety Roundup Ready (trademark of Monsanto Comp. USA) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with the tobacco budworm Heliothis virescens while the leaves are still moist.

After the desired time the kill of the insects is determined.

Claims

claims

1. Composition containing mixtures of compounds of the formula (I)

in which

X is halogen, alkyl, alkoxy, haloalkyl, haloalkoxy or cyano,

W, Y and Z independently of one another represent hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy or cyano,

A is hydrogen, in each case optionally halogen-substituted alkyl, alkoxyalkyl, saturated, optionally substituted cycloalkyl in which optionally at least one ring atom is replaced by a heteroatom,

B is hydrogen or alkyl,

A and B, together with the carbon atom to which they are attached, represent a saturated or unsaturated unsubstituted or substituted cycle, optionally containing at least one heteroatom,

D is hydrogen or an optionally substituted radical from the group consisting of alkyl, alkenyl, alkoxyalkyl, saturated cycloalkyl, in which optionally one or more ring members are replaced by heteroatoms,

A and D together with the atoms to which they are bonded represent a saturated or unsaturated and optionally at least one heteroatom-containing, unsubstituted or substituted in the A, D-part cycle,

G is hydrogen (a) or one of the groups - -

stands,

wherein

E is a metal ion or an ammonium ion,

L is oxygen or sulfur,

M is oxygen or sulfur,

RI is in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionally halogen, alkyl or alkoxy-substituted cycloalkyl which may be interrupted by at least one heteroatom, in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl stands,

R is in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or in each case optionally substituted cycloalkyl, phenyl or benzyl,

R ^{3 is} optionally halogen-substituted alkyl or optionally substituted phenyl,

R4 and RS independently of one another are each optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio or in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio and

R 1 and R 2 are independently of each other hydrogen, in each case optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, optionally substituted phenyl, or optionally substituted benzyl or together with the N-Atoni, to. they are bonded, represent an optionally substituted by oxygen or sulfur optionally substituted ring

and ethiprole. ■ -

2. Composition according to claim 1 containing compounds of formula (I) in which

W is hydrogen, C _j -C ^ alkyl, Ci-C4-alkoxy, chlorine, bromine or fluorine,

X is C _j -C 4 alkyl, C _j -C ^ alkoxy, C _j ^ -C haloalkyl, fluorine, chlorine or bromine,

Y and Z independently of one another represent hydrogen, C 1 -C 4 -alkyl, halogen, C 1 -C 4 -alkyl,

Alkoxy or C _j -C 4 haloalkyl,

A represents hydrogen or in each case optionally halogen-substituted C ₁ -C 6 -alkyl or C ₃ -CG -cycloalkyl,

B is hydrogen, methyl or ethyl,

J A, B and the carbon atom to which they are attached for saturated C3-C6

Cycloalkyl, in which optionally one ring member is replaced by oxygen or sulfur and which is optionally monosubstituted or disubstituted by C 1 -C ₄ -alkyl, trifluoromethyl or C 1 -C ₄ -alkoxy,

D represents hydrogen, in each case optionally fluorine or chlorine-substituted C _r C ₆ alkyl, C ₃ -C ₄ alkenyl or C ₃ -C ₆ cycloalkyl,

A and D together represent optionally methyl-substituted C ₃ -C ₄ alkanediyl, in which optionally a methylene group is replaced by sulfur,

G is hydrogen (a) or one of the groups _(e);

stands,

in which

E is a metal ion or an ammonium ion,

L stands for oxygen or sulfur and

M is oxygen or sulfur,

R ¹ represents in each case optionally halogen-substituted Q-Cio-alkyl, _C2 - Cio-alkenyl, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ alkyl, Ci-C ₄ alkylthio-CrC ₄ alkyl or optionally C ₃ -C -cycloalkyl which is substituted by fluorine, chlorine, C ₁ -C ₄ -alkyl or C ₁ -C ₂ -alkoxy,

optionally substituted by fluorine, chlorine, bromine, cyano, nitro, Ci-C ₄ alkyl, C _r C ₄ alkoxy, trifluoromethyl or trifluoromethoxy-substituted phenyl,

is in each case optionally substituted by chlorine or methyl substituted pyridyl or thienyl,

R ^{2 is} in each case optionally substituted by fluorine or chlorine-substituted Ci-Cio

Alkyl, C ₂ -C ₁₀ alkenyl, C _r C ₄ -alkoxy-C ₂ -C ₄ alkyl,

for optionally substituted by methyl or methoxy Cs-Cβ-cycloalkyl or

each optionally substituted by fluorine, chlorine, bromine, cyano, nitro, Cj-C ₄ - alkyl, Ci-C ₄ alkoxy, trifluoromethyl or trifluoromethoxy substituted

Phenyl or benzyl,

R ³ represents optionally fluorine-substituted Ci-C ₄ alkyl, or is optionally substituted by fluorine, chlorine, bromine, C _r C ₄ alkyl, C _r C ₄ alkoxy, - o -

Trifluoromethyl, trifluoromethoxy, cyano or nitro substituted phenyl,

R ^{4 is} in each case optionally fluorine- or chlorine-substituted C ₁ -C ₄ -

Alkyl, C ₁ -C ₄ -alkoxy, CrC ₄ alkylamino, C _r C ₄ alkylthio or optionally substituted by fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₄ -alkoxy in each case,

Trifluoromethoxy, C _r C ₄ alkylthio, C _r C ₄ haloalkylthio, C _r C ₄ alkyl or trifluoromethyl-substituted phenyl, phenoxy or phenylthio,

R ^{5 is} C _r C ₄ -alkoxy or C _r C ₄ -thioalkyl,

^R6 is Ci-Ce-alkyl, C ₃ -C ₆ cycloalkyl, C _r C ₆ alkoxy, C ₃ -C ₆ alkenyl, C ₁ -C ₄ - alkoxy-QQ-alkyl,

R ⁷ is CrCβ-alkyl, C ₃ -C ₆ alkenyl or C _r C ₄ alkoxy-C _r C alkyl _4,

R ⁶ and R ⁷ together represent an optionally substituted by methyl or ethyl C ₃ -C ₆ alkylene, in which optionally a carbon atom is replaced by oxygen or sulfur.

Composition according to claim 1 containing compounds of formula (I) in which

W is hydrogen, methyl, ethyl, chlorine, bromine or methoxy,

X is chlorine, bromine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy or trifluoromethyl,

Y and Z independently of one another represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, trifluoromethyl or methoxy,

A represents methyl, ethyl, propyl, isopropyl, buryl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclopentyl or cyclohexyl,

B is hydrogen, methyl or ethyl,

A, B and the carbon atom to which they are attached are saturated Cβ-cycloalkyl in which, where appropriate, a ring member is replaced by oxygen and which is optionally monosubstituted by methyl, ethyl, methoxy, ethoxy, propoxy or butoxy, D is hydrogen, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, AHyI ₃ cyclopropyl, cyclopentyl or cyclohexyl,

A and D together represent optionally methyl-substituted C ₃ -C ₄ alkanediyl,

G is hydrogen (a) or one of the groups

stands,

in which

M is oxygen or sulfur,

R ^{1 is} C ₁ -C ₆ -alkyl, C ₂ -C ₄ -alkenyl, methoxymethyl, ethoxymethyl, ethylthiomethyl, cyclopropyl, cyclopentyl or cyclohexyl,

optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, trifluoromethyl or trifluoromethoxy phenyl,

is in each case optionally substituted by chlorine or methyl substituted pyridyl or thienyl,

R ^{2 is} C ₁ -C ₆ -alkyl, C ₂ -C ₄ -alkenyl, methoxyethyl, ethoxyethyl or phenyl or benzyl,

R ⁶ and R ⁷ independently of one another are methyl, ethyl or together represent a C ₅ -alkylene radical in which the C ₃ -methylene group has been replaced by oxygen.

4. Composition according to claim 1 containing compounds of formula (I) in which

W is hydrogen or methyl,

X is chlorine, bromine or methyl,

Y and Z independently of one another represent hydrogen, chlorine, bromine or methyl, A, B and the carbon atom to which they are bonded, represent saturated Cβ-cycloalkyl in which optionally a ring member is replaced by oxygen and which is optionally substituted by methyl, methoxy, ethoxy, propoxy or butoxy,

D is hydrogen,

G is hydrogen (a) or one of the groups

stands,

in which

M is oxygen or sulfur,

R ^{1 is} C _r C ₈ alkyl, C ₂ -C ₄ alkenyl, methoxytnethyl, ethoxymethyl, ethylmethylthio, cyclopropyl, cyclopentyl, cyclohexyl or

optionally substituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro phenyl,

is in each case optionally substituted by chlorine or methyl substituted pyridyl or thienyl,

R ^{2 is} C ₁ -C ₆ -alkyl, C ₂ -C ₄ -alkenyl, methoxyethyl, ethoxyethyl, phenyl or benzyl,

R ⁶ and R ⁷ independently of one another represent methyl, ethyl or together represent a C ₅ -alkylene radical in which the CrMethylene group has been replaced by oxygen.

5. Composition according to claim 1 comprising compounds of the formula (I)

- -

in which

W, X, Y, Z, R and G have the meanings given in the table.

6. Use of mixtures as defined in claim 1, 1, 3, 4 and 5, for controlling animal pests.

7. A method for controlling animal pests, characterized in that mixtures, as defined in claim 1, 2, 3, 4 and 5, act on animal pests and / or their habitat.

8. A process for the preparation of insecticidal and acaricidal agents, characterized in that mixtures as defined in claim 1, 2, 3, 4 and 5, mixed with extenders and / or surface-active substances.