Patent Description:
B3)
wherein component <NUM>) and component <NUM>) are present in a weight ratio of from <NUM>:<NUM> to <NUM>:<NUM>.

One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control. Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests.

Another difficulty in relation to the use of pesticides is that the repeated and exclusive application of an individual pesticidal compound leads in many cases to a rapid selection of pests which have developed natural or adapted resistance against the active compound in question. Therefore, there is a need for pest control agents that help prevent or overcome resistance.

<CIT> and <CIT> describe N-pyridazinyl carboxamide compounds derived from pyrazole carboxylic acids. These compounds are mentioned to be useful for combating invertebrate pests.

<CIT> relates to pesticidal mixtures comprising an active anthranilamide compound. The invention relates further to methods for controlling and combating pests, such as insects, acarids or nematodes.

<CIT> discloses the method for controlling pests with an insectidcidal carboxamide compound or a mixture therof in cultivated plants which may possibly genetically modified by mutagenesis or genetic engenieering.

<CIT> relates to imino compounds with <NUM>-chloropyramidin-<NUM>-yl substitutent as pest control agents.

<CIT> discloses isoxazoline derivates with insecticidal properties and their synthesis.

<CIT> relates to insecticidal compounds derived from isoxazoline. These compounds are described in terms of their synthesis, formulation and their effectiveness for pest control.

<CIT> describes a pyrazole compound and the derivates along with their synthesis. These compounds are disclosed for their effectiveness in controlling pests.

It is therefore an object of the present invention to provide pesticidal mixtures which solve at least one of the discussed problems as reducing the dosage rate, enhancing the spectrum of activity or combining knock-down activity with prolonged control or as to resistance management.

It has been found that at least one of these objectives is achieved by the combination of active compounds defined in the outset. Moreover, it has also been found that simultaneous, that is joint or separate, application of compound A and compound B or successive application of active compound A and active compound B allows enhanced control of pests compared to the control rates that are possible with the individual compounds.

Moreover, the present invention relates to.

The mixture according to the invention may be a physical mixture of the compound A and the compound B. Accordingly, the invention also provides a mixture comprising compound A and compound B. However, the composition may also be the combination of compound A with compound B, it not being required for compounds A and B to be present together in the same formulation.

An example of a composition according to the invention or to be used according to the invention in which the compound A and the compound B are not present together in the same formulation is a combipack. In a combipack, two or more components of a combipack are packaged separately, i.e., not jointly pre-formulated. As such, combipacks include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition. One example is a two-component combipack. Accordingly the present invention also relates to a two-component combipack, comprising a first component which in turn comprises compound A, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary, and a second component which in turn comprises compound B, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary. More details, e.g. as to suitable liquid and solid carriers, surfactants and customary auxiliaries are described below.

The "combined" use of pyrazole compound A "in combination with" compound B on the one hand can be understood as using a physical mixture of pyrazole compound A and compound B. On the other hand, the combined use may also consist in using the pyrazole compound A and compound B separately, but within a sufficiently short time of one another so that the desired effect can take place. More detailed illustrations of the combined use can be found in the specifications below.

The term "invertebrate pest" (also referred to as animal pests) as used herein encompasses animal populations, such as insects, arachnids and nematodes, which may attack plants, thereby causing substantial damage to the plants attacked, as well as ectoparasites which may infest animals, in particular warm blooded animals such as e.g. mammals or birds, or other higher animals such as reptiles, amphibians or fish, thereby causing substantial damage to the animals infested.

The term "compound(s) according to the invention", or "compound(s) of formula I-<NUM>" or "pyrazole compound(s) A" comprises the compound(s) as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof. The term "compound(s) of the present invention" is to be understood as equivalent to the term "compound(s) according to the invention", therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof.

The term "stereoisomers" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one centre of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).

The compound of formula I-<NUM> has a centre of chirality, and may be present as mixture of enantiomers. The invention provides both the pure enantiomers or their mixtures and the use according to the invention of the pure enantiomers of the compound I-<NUM> or its mixtures.

The term "N-oxide" relates to a form of compound I-<NUM> in which at least one nitrogen atom is present in oxidized form (as NO).

The active compounds may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compound of the formula I-<NUM>, mixtures of different crystalline states of the respective compound I-<NUM>, as well as amorphous or crystalline salts thereof.

Salts of the compound of the formula I-<NUM> are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I-<NUM> has a basic functionality or by reacting an acidic compound of formula I-<NUM> with a suitable base.

Suitable agriculturally acceptable salts are especially the salts of those cations or the acid ad-dition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH<NUM>+) and substituted ammonium in which one to four of the hydrogen atoms are replaced by C<NUM>-C<NUM>-alkyl, C<NUM>-C<NUM>-hydroxyalkyl, C<NUM>-C<NUM>-alkoxy, C<NUM>-C<NUM>-alkoxy-C<NUM>-C<NUM>-alkyl, hydroxy-C<NUM>-C<NUM>-alkoxy-C<NUM>-C<NUM>-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, <NUM>-hydroxyethylammonium, <NUM>-(<NUM>-hydroxyethoxy)ethylammonium, bis(<NUM>-hydroxyethyl)ammonium, benzyltrimethylammonium and benzl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C<NUM>-C<NUM>-alkyl)sulfonium, and sulfoxo-nium ions, preferably tri(C<NUM>-C<NUM>-alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C<NUM>-C<NUM>-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound of formula I-<NUM> with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.

The commercially available compound B may be found in <NPL>) among other publications, and its online database https://www. org/product/bcpc-online-pesticide-manual-latest-version. CompoundBand its pesticidal action are known from <CIT>.

We have found that simultaneous, that is joint or separate, application of compound I-<NUM> and compound B or successive application of the compound of formula I-<NUM> and compound B allows better control of animal pests than is possible with the individual compounds alone (synergistic mixtures). By simultaneous, that is joint or separate, application of the compound of formula I-<NUM> with the active compound B, the fungicidal and/or insecticidal activity, resp. , is increased in a super-additive manner.

The compound of the formula I-<NUM> can be present in different crystal modifications, which may differ in biological activity.

Pesticidal mixture A comprises as active components:.

wherein component <NUM>) and component <NUM>) are present in a total weight ratio of from <NUM>:<NUM> to <NUM>:<NUM>;.

Binary mixtures of a compound of formula I-<NUM> and a compound B are one preferred embodiment of the invention.

The invention relates to mixtures of the compound A and the compound B, particularly containing additionally at least a further insecticide, which is not a compound of formula II
<CHM>
wherein.

wherein two geminally bound groups RbRb, RcRb or RcRc together with the atom to which they are bound, may form a <NUM>-, <NUM>-, <NUM>-, <NUM>-, or <NUM>- membered saturated, partially unsaturated, or aromatic carbo- or heterocyclic ring;
or a stereoisomer, tautomer, salt, or N-oxide thereof.

Compounds of formula II and its preparation are described in <CIT>.

A further embodiment of the invention relates to the mixture A, containing additionally at least a fungicide C from the groups F1 to F11.

wherein component A and component C are present in a weight ratio from <NUM>:<NUM> to <NUM>:<NUM>, and component B and C are present in a weight ratio from <NUM>:<NUM> to <NUM>:<NUM>.

Ternary mixtures of a mixture A and a fungicide C from the groups F. <NUM> to F. <NUM> are another preferred embodiment of the invention. The ternary mixtures of the present invention have excellent activity against a broad spectrum of phytopathogenic fungi and animal pests.

The mixtures of the present invention have excellent activity against a broad spectrum of animal pests.

They are in particular suitable for efficiently controlling invertebrate pests. Particular, they are suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.

In particular, they are suitable for controlling insect pests, such as insects from the order of lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis;.

They are also suitable for controlling nematodes : plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Helio-cotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.

They are also useful for controlling arachnids (Arachnoidea), such as acarians (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.

The ternary mixtures comprising a fungicide C have excellent activity against a broad spectrum of phytopathogenic fungi Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). Some of them are systemically effective and can be employed in crop protection as foliar fungicides, as fungicides for seed dressing and as soil fungicides. They can also be used for treating seed.

They are particularly important in the control of a multitude of fungi on various cultivated plants, such as wheat, rye, barley, oats, rice, corn, lawns, bananas, cotton, soybean, coffee, sugar cane, grapevines, fruits and ornamental plants, and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.

They are especially suitable for controlling the following plant diseases:.

The mixtures according to the invention are also suitable for controlling Lepidoptera, Coleoptera, Diptera, Thysanoptera and Hemiptera. In particular, the mixtures are useful for the control of Thysanoptera and Hemiptera, especially Hemiptera.

The present invention relates to the pesticidal mixture A which is particularly suitable for controlling pests from the family of Pentatomidae and/or Cicadellidae and/or Aleyrodidae and/or Aphididae, which are typical pests on soybean plants.

In one preferred embodiment, the present invention relates to the use or method comprising the application of the pesticidal mixtures as defined above, wherein the pests are selected from the group consisting of green stink bug (Acrosternum hilare), brown marmorated stink bug (Halyomorpha halys), redbanded stink bug (Piezodorus guildinii), neotropical brown stink bug (Euschistus heros), brown stink bug (Euschistus servus), kudzu bug (Megacopta cribraria), red-shouldered stink bug (Thyanta custator) and the dusky-brown stink bug (Euschistus tristigmus), the southern green stink bug (Nezara viridula), and combinations thereof.

In one embodiment the stinkbug target is Nezara viridula, Piezodorus spp. , Acrosternum spp. Euschistus and in particular Euchistus heros are the preferred targets. More preferably the pesticidal mixtures are used to control Pentatomidae including green stink bug (Acrosternum hilare), brown marmorated stink bug (Halyomorpha halys), redbanded stink bug (Piezodorus guildinii), neotropical brown stink bug (Euschistus heros), brown stink bug (Euschistus servus), and kudzu bug (Megacopta cribraria), red-shouldered stink bug (Thyanta custator), dusky-brown stink bug (Euschistus tristigmus), and southern green stink bug (Nezara viridula).

Furthermore, the pesticidal mixture A is particularly suitable for controlling pests Aleyrodidae including sweetpotato whitefly (Bemisia tabaci), Aphididae including cotton aphid (Aphis gossypii) and soybean aphid (Aphis glycines) and combinations thereof.

In another embodiment, the pests are Thyanta custator.

In another embodiment, the pests are Euschistus tristigmus.

In another embodiment, the pests are Acrostemum hilare.

In another embodiment, the pests are Halyomorpha halys.

In another embodiment, the pests are Piezodorus guildinii.

In another embodiment, the pests are Euschistus heros.

In another embodiment, the pests are Euschistus servus.

In another embodiment, the pests are Megacopta cribraria.

In another embodiment, the pests are Nezara viridula.

In another embodiment, the pests are Bemisia tabacii.

In another embodiment, the pests are Aphis gossypii.

In another embodiment, the pests are Aphis glycines.

In another embodiment, the pests are Amrasca biguttula biguttula.

In another embodiment, the pests are Empoasca fabae.

In another embodiment, the pests are Epoasca kraemeri.

The pesticidal mixture A is preferably used on Faboideae, in particular soybean, to control stinkbugs, e.g. Nezara spp. (e.g. Nezara viridula, Nezara antennata, Nezara hilaris), Piezodorus spp. (e.g. Piezodorus guildinii), Acrosternum spp. (e.g. Acrosternum hilare), Euchistus spp. (e.g. Euchistus heros, Euschistus servus), Halyomorpha halys, Megacopta cribaria, Plautia crossota, Riptortus clavatus, Rhopalus msculatus, Antestiopsis orbitalus, Dectes texanus, Dichelops spp. (e.g. Dichelops furcatus, Dichelops melacanthus), Eurygaster spp. (e.g. Eurygaster intergriceps, Eurygaster maurd), Oebalus spp. (e.g. Oebalus mexicana, Oebalus poecilus, Oebalus pugnase, Scotinophara spp. (e.g. Scotinophara lurida, Scotinophara coarctatd).

Preferred targets include Acrosternum hilare, Antestiopsis orbitalus, Dichelops furcatus, Dichelops melacanthus, Euchistus heros, Euschistus servus, Megacopta cribaria, Nezara viridula, Nezara hilare, Piezodorus guildinii, Halyomorpha halys.

Further Pentatomidae pests that can be controlled according to the invention are Eysarcoris, in particular Eysarcoris aeneus.

The mixtures are preferably used on Faboideae, in particular soybean, to control whiteflies, e.g. sweetpotato whitefly (Bemisia tabaci).

The mixtures are preferably used on Faboideae, in particular soybean, to control aphids, e.g. soybean aphid (Aphis glycines).

The mixtures are preferably used on Faboideae, in particular soybean, to control leafhoppers, e.g. potato leafhopper (Empoasca fabae).

The mixtures are preferably used on Faboideae, in particular soybean, to control leafhoppers, e.g. Lorito verde (small green pakeet) (Empoasca kraemeri).

The pesticidal mixture A is preferably used to control lepidopterans (Lepidoptera), such as Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura; beetles (Coleoptera), such as Anthonomus grandis, Anthonomus pomorum, and thrips (Thysanoptera), such as Scirtothrips citri.

The pesticidal mixture can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the active compounds.

The pesticidal mixture can be converted into customary types of agro-chemical compositions, e. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "<NPL>.

The compositions are prepared in a known manner, such as described by <NPL>; or <NPL>.

Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in<NPL>.

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with <NUM> to <NUM> equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpoly-glucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the active compounds on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by <NPL>.

Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

Examples for composition types and their preparation are:.

The compositions types i) to xi) may optionally comprise further auxiliaries, such as <NUM>-<NUM> wt% bactericides, <NUM>-<NUM> wt% anti-freezing agents, <NUM>-<NUM> wt% anti-foaming agents, and <NUM>-<NUM> wt% colorants.

The agrochemical compositions generally comprise between <NUM> and <NUM>%, preferably between <NUM> and <NUM>%, and most preferably between <NUM> and <NUM>%, by weight of active substance. The active substances are employed in a purity of from <NUM>% to <NUM>%, preferably from <NUM>% to <NUM>% (according to NMR spectrum).

Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of <NUM>:<NUM> to <NUM>:<NUM>, preferably <NUM>:<NUM> to <NUM>:<NUM>.

The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, <NUM> to <NUM> liters, preferably <NUM> to <NUM> liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.

In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. components comprising compounds of the present invention and/or mixing partners as defined above, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.

In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. components comprising compounds of the present invention and/or mixing partners as defined above, can be applied jointly (e.g. after tank mix) or consecutively.

The mixtures of the present invention are employed as such or in form of compositions by treating the insects, the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with a pesticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.

The present invention also includes a non-therapeutic method of combating animal pests and harmful fungi which comprises contacting the fungi and/or animal pests, their habit, breeding ground, food supply, cultivated plants, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of a mixture according to the invention. The mixtures or compositions of these mixtures can also be employed for protecting plants from attack or infestation by invertebrate pests such as insects, acarids or nematodes comprising contacting a plant, or soil or water in which the plant is growing.

The pyrazole compound A and compound B are applied in a weight ratio of from <NUM>:<NUM> to <NUM>:<NUM>, preferably from <NUM>:<NUM> to <NUM>:<NUM>, more preferably from <NUM>:<NUM> to <NUM>:<NUM>, in particular from <NUM>:<NUM> to <NUM>:<NUM>.

In ternary mixtures the pyrazole compound A selected from compound I-<NUM> and B are usually present in ratio ranges of from <NUM>:<NUM>:<NUM>, to <NUM>:<NUM>:<NUM> to <NUM>:<NUM>:<NUM> to <NUM>:<NUM>:<NUM> to <NUM>:<NUM>:<NUM> to <NUM>:<NUM>:<NUM>.

Depending on the desired effect, the application rates of the mixtures of the invention are from <NUM>/ha to <NUM>/ha, preferably from <NUM> to <NUM>/ha, in particular from <NUM> to <NUM>/ha.

The mixtures according to the invention are effective through both contact and ingestion. According to a preferred embodiment of the invention, the mixtures according to the present invention are employed via soil application. According to a further preferred embodiment of the invention, the mixtures of the present invention are employed via soil application. Soil application is especially favorable for use against ants, termites, crickets, or cockroaches.

According to another preferred embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the mixtures according to the present invention are prepared into a bait preparation. The mixtures of the invention may also be applied against said non-crop pests.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).

Another aspect of the present invention is when preparing the mixtures, it is preferred to employ the pure active compounds I-<NUM> and B, to which further active compounds, e.g. against harmful fungi or having herbicidal activity, or growth-regulating agents or fertilizers can be added.

Compositions comprising the inventive mixture may further contain other active ingredients than those listed above. Compositions of this invention may further contain other active ingredients than those listed above. For example fungicides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.

The mixtures according to the invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the inventive mixtures or of compositions comprising the mixtures.

"Locus" means a plant, seed, soil, area, material or environment in which a pest is growing or may grow.

In general, "pesticidally effective amount" means the amount of the inventive mixtures or of compositions comprising the mixtures needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various mixtures and/or compositions used in the invention. A pesticidally effective amount of the mixtures and/or compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

The mixtures or compositions of these mixtures can also be employed for protecting plants from attack or infestation by invertrebrate pests such as insects, acarids or nematodes comprising contacting a plant, or soil or water in which the plant is growing.

The inventive mixtures are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part) and through trophallaxis and transfer.

Preferred application methods are into water bodies, via soil, cracks and crevices, pastures, manure piles, sewers, into water, on floor, wall, or by perimeter spray application and bait. According to another preferred embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the inventive mixtures are prepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it. This attractant may be chosen from feeding stimulants or para and / or sex pheromones readily known in the art.

Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with the inventive mixtures and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibres, fabric, knitgoods, non-wovens, netting material or foils and tarpaulins preferably comprise a composition including the inventive mixtures, optionally a repellent and at least one binder.

The mixtures and the compositions comprising them can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).

In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient(s) ranges from <NUM> to <NUM> per <NUM><NUM>, preferably from <NUM> to <NUM> per <NUM><NUM>.

Customary application rates in the protection of materials are, for example, from <NUM> to <NUM> of active compounds per m<NUM> treated material, desirably from <NUM> to <NUM> per m<NUM>.

Insecticidal compositions for use in the impregnation of materials typically contain from <NUM> to <NUM> weight %, preferably from <NUM> to <NUM> weight %, and more preferably from <NUM> to <NUM> weight % of at least one repellent and / or insecticide.

For use in bait compositions, the typical content of active ingredient(s) is from <NUM> weight % to <NUM> weight %, desirably from <NUM> weight % to <NUM>% weight % of active compound. The composition used may also comprise other additives such as a solvent of the active material, a flavoring agent, a preserving agent, a dye or a bitter agent. Its attractiveness may also be enhanced by a special color, shape or texture.

For use in spray compositions, the content of the mixture of the active ingredients is from <NUM> to <NUM> weights %, preferably from <NUM> to <NUM> weight % and most preferably from <NUM> to <NUM> weight %.

For use in treating crop plants, the rate of application of the mixture of the active ingredients of this invention may be in the range of <NUM> to <NUM> per hectare, desirably from <NUM> to <NUM> per hectare, more desirably from <NUM> to <NUM> per hectare.

In the context of the present invention, the term plant refers to an entire plant, a part of the plant or the plant propagation material.

The mixtures of the present invention and the compositions comprising them are particularly important in the control of a multitude of insects on various cultivated plants.

Plants which can be treated with the inventive mixtures include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures.

The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be mentioned. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.

The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.

The term "cultivated plants" is to be understood also including plants that have been rendered tolerant to applications of specific classes of herbicides, such as hydroxy-phenylpyruvate dioxy-genase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>) or imidazolinones (see e. <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>); enolpyruvylshikimate-<NUM>-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. <CIT>); glutamine synthetase (GS) inhibitors, such as glufosinate (see e. <CIT>, <CIT>) or oxynil herbicides (see e. <CIT>) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield® summer rape (Canola) being tolerant to imidazolinones, e. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).

The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ -endotoxins, e. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CryIIIA, CryllIB(b1) or Cry9c; vegetative insecticidal proteins (VIP), e. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp. ; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as <NUM>-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, for example <CIT>). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are dis-closed, for example, in <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT> und <CIT>. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of insects, especially to beetles (Coeloptera), two-winged insects (Diptera), and butterflies (Lepidoptera).

The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to in-crease the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, for example <CIT>), plant disease resistance genes (for example potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environ-mental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.

The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e.g. oil crops that produce health-promoting long-chain omega-<NUM> fatty acids or unsaturated omega-<NUM> fatty acids (e. Nexera® rape). The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e.g. potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato).

Some of the inventive mixtures have systemic action and can therefore be used for the protection of the plant shoot against foliar pests as well as for the treatment of the seed and roots against soil pests.

The mixtures according to the present invention are therfore suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect pests and the resulting plants' roots and shoots against soil pests and foliar insects.

The protection of the resulting plant's roots and shoots is preferred.

More preferred is the protection of resulting plant's shoots from piercing and sucking insects. The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedlings' roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with mixtures according to the present invention. Particularly preferred is a method, wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected from piercing and sucking insects, most preferably a method, wherein the plants shoots are protected from aphids.

The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.

The term seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.

The present invention also comprises seeds coated with or containing the active compounds. The term "coated with and/or containing" generally signifies that the active ingredient(s) are for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation products are (re)planted, it may absorb the active ingredient.

Suitable seeds are seeds of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

In addition, the mixtures according to the invention may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.

For example, the active mixtures can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, <CIT>, <CIT>) (<CIT>) (<CIT>, <CIT>) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (<CIT>, <CIT>).

Furthermore, the mixtures according to the present invention can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures). a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. <CIT>, <CIT>, <CIT>) or of transgenic crop plants having a modified fatty acid composition (<CIT>).

The seed treatment application of the mixtures is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.

In the treatment of seeds the corresponding formulations are applied by treating the seeds with an effective amount of the mixtures of the invention. Herein, the application rates of the active compounds are generally from <NUM>,<NUM> to <NUM> per <NUM> of seed, preferably from <NUM> to <NUM> per <NUM> of seed, in particular from <NUM> to <NUM>,<NUM> per <NUM> of seed. For specific crops such as lettuce the rate can be higher.

Compositions, which are especially useful for seed treatment are e.g.:.

Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter.

In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise <NUM>-<NUM>/l of active ingredient(s), <NUM>-<NUM>/l Surfactant, <NUM> to <NUM>/l antifreezing agent, <NUM> to <NUM>/l of binder, <NUM> to <NUM>/l of a pigment and up to <NUM> liter of a solvent, preferably water.

Preferred FS formulations of mixtures for seed treatment usually comprise from <NUM> to <NUM>% by weight (<NUM> to <NUM>/l) of the active ingredients, from <NUM> to <NUM> % by weight (<NUM> to <NUM>/l) of at least one surfactant, e.g. <NUM> to <NUM> % by weight of a wetter and from <NUM> to <NUM> % by weight of a dispersing agent, up to <NUM> % by weight, e.g. from <NUM> to <NUM> % of an anti-freeze agent, from <NUM> to <NUM> % by weight, e.g. <NUM> to <NUM> % by weight of a pigment and/or a dye, from <NUM> to <NUM> % by weight, e.g. <NUM> to <NUM> % by weight of a binder (sticker /adhesion agent), optionally up to <NUM> % by weight, e.g. from <NUM> to <NUM> % by weight of a thickener, optionally from <NUM> to <NUM> % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from <NUM> to <NUM> % by weight and a filler/vehicle up to <NUM> % by weight.

Seed treatment formulations may additionally also comprise binders and optionally colorants. Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are block copolymers EO/PO surfactants but also polyvinylalcoholsl, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, tylose and copolymers derived from these polymers.

Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C. Pigment Red <NUM>, C. Solvent Red <NUM>, pigment blue <NUM>:<NUM>, pigment blue <NUM>:<NUM>, pigment blue <NUM>:<NUM>, pigment blue <NUM>:<NUM>, pigment blue <NUM>, pigment yellow <NUM>, pigment yellow <NUM>, pigment red <NUM>, pigment red <NUM>:<NUM>, pigment red <NUM>:<NUM>, pigment red <NUM>:<NUM>, pigment red <NUM>:<NUM>, pigment orange <NUM>, pigment orange <NUM>, pigment orange <NUM>, pigment green <NUM>, pigment green <NUM>, pigment white <NUM>, pigment brown <NUM>, basic violet <NUM>, basic violet <NUM>, acid red <NUM>, acid red <NUM>, acid red <NUM>, acid blue <NUM>, acid yellow <NUM>, basic red <NUM>, basic red <NUM>.

The invention also relates to seed comprising mixtures according to the invention. The amount of the mixture or the agriculturally useful salt thereof will in general vary from <NUM> to <NUM> per <NUM> of seed, preferably from <NUM> to <NUM> per <NUM> of seed, in particular from <NUM> to <NUM> per <NUM> of seed.

The mixtures of the invention are in particular also suitable for being used for combating parasites in and on animals.

An object of the present invention is therfore also to provide new methods to control parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.

The present invention also provides a mixture for use in a therapeutic method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of the mixture of the present invention or a composition comprising it.

The disclosure also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a mixture of the present invention or a composition comprising it.

Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.

Surprisingly it has now been found that mixtures of the present invention are suitable for combating endo- and ectoparasites in and on animals.

Mixtures of the present invention and compositions comprising them are preferably used for controlling and preventing infestations and infections animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.

Mixtures of the present invention and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.

Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas.

The mixtures of the present invention and compositions comprising them are suitable for systemic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.

The mixtures of the present invention are especially useful for combating ectoparasites.

The mixture of the present invention is especially useful for combating parasites of the following orders and species, respectively:.

The mixtures of the invention and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.

Moreover, the mixtures of the invention and compositions containing them for combating mosquitoes is especially preferred.

The use of mixtures of the invention and compositions containing them for combating flies is a further preferred embodiment of the present invention.

Furthermore, the use of the mixtures of the invention and compositions containing them for combating fleas is especially preferred.

The mixtures of the invention and compositions containing them for use in a method of treatment for combating ticks is a further preferred embodiment of the present invention.

The mixtures of the present invention also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).

Administration can be carried out both prophylactically and therapeutically.

Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.

For oral administration to warm-blooded animals, the mixtures of the present invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the mixtures of the present invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with <NUM>/kg to <NUM>/kg of animal body weight per day of the formula I-<NUM> compound, preferably with <NUM>/kg to <NUM>/kg of animal body weight per day.

Alternatively, the mixtures of the present invention may be administered to animals parenterally, e.g., by intraruminal, intramuscular, intravenous or subcutaneous injection. The mixture compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the mixtures of the present invention may be formulated into an implant for subcutaneous administration. In addition the mixture compounds may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with <NUM>/kg to <NUM>/kg of animal body weight per day of the active compounds.

The mixtures of the invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain <NUM> ppm to <NUM>,<NUM> ppm and preferably <NUM> ppm to <NUM>,<NUM> ppm of the active compounds. In addition, the active compound mixtures may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.

Compositions suitable for injection are prepared by dissolving the active ingredients in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile.

Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N-methyl-pyrrolidone, <NUM>-pyrrolidone, and mixtures thereof.

The active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.

Suitable solubilizers are solvents which promote the dissolution of the active compounds in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.

Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.

Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.

Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.

Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.

It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.

Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results.

The thickeners employed are the thickeners given above.

Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compounds penetrating the skin and acting systemically.

Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compounds in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added.

Suitable solvents which are: water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, N-alkylpyrrolidones such as methylpyrrolidone, N-butylpyrrolidone or N-octylpyrrolidone, N-methylpyrrolidone, <NUM>-pyrrolidone, <NUM>,<NUM>-dimethyl-<NUM>-oxy-methylene-<NUM>,<NUM>-dioxolane and glycerol formal.

Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.

Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.

Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.

Suitable light stabilizers are, for example, novantisolic acid.

Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacrylates, natural polymers such as alginates, gelatin.

Emulsions can be administered orally, dermally or as injections.

Emulsions are either of the water-in-oil type or of the oil-in-water type.

They are prepared by dissolving the active compounds either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances.

Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.

Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.

Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compounds in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.

Liquid suspending agents are all homogeneous solvents and solvent mixtures.

Suitable wetting agents (dispersants) are the emulsifiers given above.

Other auxiliaries which may be mentioned are those given above.

Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.

For the production of solid preparations, the active compounds are mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.

Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.

Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.

Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.

In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.

The compositions which can be used in the invention can comprise generally from about <NUM> to <NUM> wt% of the active compounds of the mixtures of the present invention.

Generally it is favorable to apply the active compounds of the mixtures of the present invention in total amounts of <NUM>/kg to <NUM>/kg per day, preferably <NUM>/kg to <NUM>/kg per day.

Ready-to-use preparations contain the active compounds of the mixtures of the present invention acting against parasites, preferably ectoparasites, in concentrations of <NUM> ppm to <NUM> per cent by weight, preferably from <NUM> to <NUM> per cent by weight, more preferably from <NUM> to <NUM> per cent by weight, most preferably from <NUM> to <NUM> per cent by weight.

Preparations which are diluted before use contain the active compounds of the mixtures of the present invention acting against ectoparasites in concentrations of <NUM> to <NUM> per cent by weight, preferably of <NUM> to <NUM> per cent by weight.

Furthermore, the preparations comprise the mixtures of the present invention against endoparasites in concentrations of <NUM> ppm to <NUM> per cent by weight, preferably of <NUM> to <NUM> per cent by weight, very particularly preferably of <NUM> to <NUM> per cent by weight.

In a preferred embodiment of the present invention, the compositions comprising the mixtures of the present invention are applied dermally / topically.

In a further preferred embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.

Generally it is favorable to apply solid formulations which release the active compounds of the mixtures of the present invention in total amounts of <NUM>/kg to <NUM>/kg, preferably <NUM>/kg to <NUM>/kg, most preferably <NUM>/kg to <NUM>/kg body weight of the treated animal in the course of three weeks.

For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the compound of formula I-<NUM>. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in <CIT>.

The present invention is now illustrated in further details by the following examples. Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds. The presence of a synergistic effect in terms of percent control or efficacy, between two mixing partners (X and Y) can be calculated using the Colby equation (<NPL>): <MAT>.

When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.

The following tests can demonstrate the control efficacy of mixtures or compositions of this invention on specific pests and fungi. However, the pest control protection afforded by the compounds, mixtures or compositions is not limited to these species. In certain instances, combinations of a compound of this invention with other invertebrate pest control compounds or agents are found to exhibit synergistic effects against certain important invertebrate pests and/or harmful fungi.

The expected efficacies of active compound mixtures were determined using Colby's formula [<NPL>)] and compared with the observed efficacies.

If not otherwise specified, the test solutions are prepared as follows:
The active compound is dissolved at the desired concentration in a mixture of <NUM>:<NUM> (vol:vol) distilled water : acteone. The test solution is prepared at the day of use.

Test solutions are prepared in general at concentrations of <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm and <NUM> ppm (wt/vol).

For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of <NUM>-well-microtiter plates containing broad bean leaf disks. The compounds or mixtures were formulated using a solution containing <NUM>% water and <NUM>% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the leaf disks at <NUM>. 5µI, using a custom built micro atomizer, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

After application, the leaf disks were air-dried and <NUM> - <NUM> adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at <NUM> ± <NUM>, <NUM> ± <NUM> % RH for <NUM> days. Aphid mortality and fecundity was then visually assessed.

For evaluating control of Caenorhabditis elegans through contact or systemic means the test unit consisted of <NUM>-well-microtiter plates containing a liquid diet.

The compounds or mixtures were formulated using a solution containing <NUM>% water and <NUM>% DMSO. Different concentrations of formulated compounds or mixtures were sprayed into the microtiter plate wells at 5µl per well, using a custom built micro atomizer, at two replications. Mixed instar <NUM>-<NUM> C. elegans were transferred into the microtiter plate wells. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

After application, the nematodes were incubated at <NUM> + <NUM>, <NUM> + <NUM> % RH for <NUM> days. Nematode motility (mortality) was then visually assessed.

For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of <NUM>-well-microtiter plates containing liquid artificial diet under an artificial membrane. The compounds or mixtures were formulated using a solution containing <NUM>% water and <NUM>% DMSO. Different concentrations of formulated compounds or mixtures were pipetted into the aphid diet, using a custom built pipetter, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

After application, <NUM> - <NUM> adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at <NUM> + <NUM>, <NUM> + <NUM> % RH for <NUM> days. Aphid mortality and fecundity was then visually assessed.

For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of <NUM>-well-microtiter plates containing an insect diet and <NUM>-<NUM> A. grandis eggs. The compounds or mixtures were formulated using a solution containing <NUM>% water and <NUM>% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 20µl, using a custom built micro atomizer, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

After application, microtiter plates were incubated at <NUM> + <NUM>, <NUM> + <NUM> % RH for <NUM> days. Egg and larval mortality was then visually assessed.

For evaluating control of Mediterranean fruitfly (Ceratitis capitata) the test unit consisted of <NUM>-well-microtiter plates containing an insect diet and <NUM>-<NUM> C. capitata eggs.

The compounds or mixtures were formulated using a solution containing <NUM>% water and <NUM>% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 5µl, using a custom built micro atomizer, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

After application, microtiter plates were incubated at <NUM> ± <NUM>, <NUM> ± <NUM> % RH for <NUM> days. Egg and larval mortality was then visually assessed.

For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of <NUM>-well-microtiter plates containing an insect diet and <NUM>-<NUM> H. virescens eggs.

The compounds or mixtures were formulated using a solution containing <NUM>% water and <NUM>% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 10µl, using a custom built micro atomizer, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

For evaluating control of yellow fever mosquito (Aedes aegypti) the test unit consisted of <NUM>-well-microtiter plates containing 200µl of tap water per well and <NUM>-<NUM> freshly hatched A. aegypti larvae.

The compounds or mixtures were formulated using a solution containing <NUM>% water and <NUM>% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at <NUM>. 5µI, using a custom built micro atomizer, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

After application, microtiter plates were incubated at <NUM> + <NUM>, <NUM> + <NUM> % RH for <NUM> days. Larval mortality was then visually assessed.

For evaluating control of Greenhouse Whitefly (Trialeurodes vaporariorum) the test unit consisted of <NUM>-well-microtiter plates containing a leaf disk of egg plant leaf disk with white fly eggs. The compounds or mixtures were formulated using a solution containing <NUM>% water and <NUM>% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at <NUM>. 5µI, using a custom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

Claim 1:
Pesticidal mixtures comprising as active components
<NUM>) pyrazole compound A, which is <NUM>-(<NUM>,<NUM>-dimethylpropyl)-N-ethyl-<NUM>-methyl-N-pyridazin-<NUM>-yl-pyrazole-<NUM>-carboxamide,
<CHM>
and
<NUM>) one further compound B, which is <NUM>-[(<NUM>)-<NUM>-(<NUM>,<NUM>-dichloro-<NUM>-fluoro-phenyl)-<NUM>-(trifluoromethyl)-<NUM>-isoxazol-<NUM>-yl]-N-[(4R)-<NUM>-ethyl-<NUM>-oxo-isoxazolidin-<NUM>-yl]-<NUM>-methyl-benzamide;
wherein component <NUM>) and component <NUM>) are present in a weight ratio of from <NUM>:<NUM> to <NUM>:<NUM>.