WO2011161040A1 - Pesticidal composition comprising a benzoylurea compound and chlorfenapyr and their uses. - Google Patents

Abstract

Pesticidal composition comprising a benzoylurea compound and chlorfenapyr and their uses The present invention relates to pesticidal compositions comprising insecticidal benzoylurea compound of the formula I and the compound of the formula II in synergistically effective amounts. The compounds of formula I and II according to the present invention are defined by the following formulea: - compound of formula I: wherein R, R¹, R², R³, n, R⁴, R⁵ are defined as in the description; - compound of formula II: The invention also relates to the use of the compositions for combating controlling, combating invertebrate pests. Furthermore the invention relates also to methods of applying such compositions.

Description

Pesticidal composition comprising a benzoylurea compound and chlorfenapyr and their uses.

The invention relates to a pesticidal composition comprising an insecticidal benzoylurea compound of the formula I and a compound of the formula II as defined hereinafter and the use of such composition for controlling invertebrate pests.

In spite of the commercial insecticides, acaricides and nematicides available today, damage to crops, both growing and harvested, caused by insects, arachnids and nematodes still occur. Therefore, there is a continuing need to develop new insecticidal, acaricidal and nematicidal agents.

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 unfavourable environmental or toxico- logical effects whilst still allowing effective pest control.

Another problem encountered concerns the need to have available pest control agents which are highly effective against a broad spectrum of pests.

There also exists the need for pest control agents that combine know-how activity with prolonged control, that is, fast action with long lasting action.

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.

It was therefore an object of the present invention to provide new pesticidal agents and new methods for the control of insects, arachnids or nematodes and of protecting growing plants from attack or infestation by insects, arachnids or nematodes and also new methods for the protection of seeds from insects.

It was therefore an object of the invention to provide pesticidal agents which solve at least one of the discussed problems as reducing the dosage rate and/or enhancing the spectrum of activity and/or combining know-how activity with prolonged control and/or to resistance manage- ment.

The benzoylurea compounds of formula (I) are for example known from US 5874615 or EP 0161019 as well as their pesticidal activity.

US 4698365 and US 4623658 disclose benzoylurea compounds having pesticidal activities, particularly insecticidal and acaricidal properties. EP 0347488 describes chlorfenapyr and derivatives compounds and their use in mixtures with other insecticides is mentioned. US 4666942 discloses methods of uses of benzoylurea compounds as insecticidal and compositions comprising the benzoylurea in combination with other compounds having pesticidal properties particularly insecticides of the order of organophosphates and pyrethroids.

CN 1364413 discloses compositions having insecticidal activities comprising chlorfenapyr and one or more selected insecticidal compounds.

JP 2006056810 discloses pesticidal compositions comprising a benzoylurea compounds and their method for harmful insects living in water is also mentioned. The need of an efficient composition having effective and high insecticidal activity is still desirable in order to combat harmful insects which can cause a great damage to crops and other plants and solve the problems above mentioned.

We have found that these objects in part or in whole are achieved by the combination of active compounds as defined in the following. Moreover, we have found that simultaneous, that is jointly or separate, application of active compound of formula I and compound of formula II or successive application of compounds I and II allows enhanced control of pests compared to the control rates that are possible with the individual compounds. Surprisingly, it has now been found that, by mixing a benzoylurea of formula I with the active compound of formula II, the objects of the invention can be achieved at least in certain aspects.

Accordingly, one aspect of the invention is the provision of a pesticidal composition comprising, as active components,

1 ) a benzoylurea compound of the formula I

wherein

R is halogen, Ci-C4 alkyl, C1-C4 alkoxy or C1-C4 alkylthio;

R¹ is hydrogen, halogen, Ci-C4 alkyl, C1-C4 alkoxy or C1-C4 alkylthio

R² is fluorine;

R³ is hydrogen, halogen, nitro, cyano, Ci-C4 alkyl or C1-C4 haloalkyl; n is an integer of 0, 1 , 2 or 3;

R⁴ is halogen or OR⁵; and

R⁵ is C1-C4 haloalkyl, C3-C7 halocycloalkyl, phenyl which may be or not substituted with up to three groups independently selected from halogen, C1-C4 haloalkyl groups, cyano groups or nitro groups, 2-pyridyl which may be or not substituted with up to three groups independently selected from halogen atoms, C1-C4 haloalkyl groups, cyano groups or nitro groups;

or an agriculturally acceptable salt thereof; and

2) a compound of the formula II

or an agriculturally acceptable salt thereof; in synergistically effective amounts.

The common name of the compound of formula II is chlorfenapyr, i.e. 4-bromo-2-(4- chlorophenyl)-1 -(ethoxymethyl)-5-(trifluoromethyl)-1 H-pyrrole-3-carbonitrile.

We have accordingly found that several objects can be achieved by the compositions as defined in the present application, i.e. by combining at least one benzoylurea compound of formula I with the compound of formula II.

Moreover, this invention relates to methods for combating and/or controlling pests, particularly invertebrate pests, insects, arachnids or nematodes by using compositions comprising compounds of formula I and II in synergistically effective amount and to a method for preparing such compositions.

Further, the present invention relates to method for treating and/or protecting plants from attack or infestation pests comprising contacting the plant, or soil or water in which the pest is growing with the composition according to the present invention. Moreover, the present invention also relates to a method of protecting plant propagation material and/or the plants which grow there from, which method comprises treating the plant propagation material with a composition according to the present invention. Further, this invention relates to the use of a composition comprising a compound of formula I and a compound of formula II for the protection of seeds and to a method of protection of seed comprising contacting the seeds before sowing and/or after pregermination with the inventive composition.

As used herein, the term "pest" is considered to include any harmful organisms including insects, acarids, and nematodes. The term "Ci-C4 alkyl", as used herein as such as well as in related terms, such as Ci-C4 alkoxy, C1-C4 haloalkyi or C1-C4 haloalkoxy, refers to straight or branched aliphatic alkyl groups having from 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

The term "halogen", as used herein as such as well as in related terms, such as "haloalkyi" or "haloalkoxy", is selected from fluorine (F), chlorine (CI), iodine (I) and bromine (Br), preferably from fluorine and chlorine, and more preferably is fluorine.

The term "Ci-C4 alkoxy" as used herein refers to a C1-C4 alkyl group, as defined above, which is linked via an oxygen atom, e.g. methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.

The term "C1-C4 haloalkyi" as used herein refers to a C1-C4 alkyl group, as defined above, which additionally contains one or more, e.g. 2, 3, 4, 5 or 6, halogen atom(s), as defined above, e.g. mono- di- and trifluoromethyl, mono-, di- and trichloromethyl, 1 -fluoroethyl, 1 -chloroethyl, 2- fluoroethyl, 2-chloroethyl, 1 ,1 -difluoroethyl, 1 ,1 -dichloroethyl, 1 ,2-difluoroethyl, 1 ,2-dichloroethyl, 2,2-difluoroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl and 2,2,2-trichloroethyl.

The term "C1-C4 haloalkoxy" as used herein refers to a Ci-C4 alkoxy group, as defined above, which additionally contains one or more, e.g. 2, 3, 4, 5 or 6, halogen atom(s), as defined above, e.g. mono- di- and trifluoromethoxy, mono- di- and trichloromethoxy, 1 -fluoroethoxy, 1 - chloroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 1 ,1 -difluoroethoxy, 1 ,1 -dichloroethoxy, 1 ,2- difluoroethoxy, 1 ,2-dichloroethoxy, 2,2-difluoroethoxy, 2,2-dichloroethoxy, 2,2,2-trifluoroethoxy and 2,2,2-trichloroethoxy. The term "Ci-C2-alkylthio" as used herein refers to a Ci-C4-alkyl group, as defined above, attached via a sulfur atom.

The term "C3-C6-cycloalkyl" as used herein refers to mono- or bi- or polycyclic saturated hydrocarbon radicals having 3 to 6 carbon atoms. Examples of monocyclic radicals having 3 to 6 car- bon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term "C3-C6-halocycloalkyl" as used herein, which is also expressed as "C3-C6-cycloalkyl which may be substituted by halogen", and the halocycloalkyl moieties in halocycloalkoxy, halo- cycloalkylcarbonyl and the like refers to mono- or bi- or polycyclic saturated hydrocarbon groups having 3 to 6 ("C3-C6-halocycloalkyl" ) carbon ring members (as mentioned above) in which some or all of the hydrogen atoms are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.

In a preferred embodiment of this invention, the substituents R¹, R², R³ and R⁴ in the benzoy- lurea compound of formula (I) independently of one another, but in particular in combination, have the preferred meanings given below:

R is F, CI or OCH₃, preferably F;

R¹ is H, F, CI or CH₃, preferably F;

R³ is H, F or CI, preferably hydrogen (H);

R⁴ F, CI or OR⁵, preferably OR⁵

R⁵ is C1-C4 haloalkyl, phenyl substituted with one to three halogen atoms or CF3 groups, preferably a 4-(trifluoromethyl)phenyl group which may be substituted by halogen.

In a preferred embodiment, preference is given to pesticidal composition wherein the benzoy- lurea compound of the formula I is flufenoxuron, i.e. compound of formula I wherein R and R¹ are F, R³ is hydrogen and R⁴ is 2-CI-4-CF3-phenoxy (i.e. CF3 which is disposed in the para position and CI in the ortho position of the phenoxy group). Flufenoxuron is the common name for 1 - [4-(A/-[[[4-[2-chloro-4-(trifluoromethyl)phenoxy]-2-fluorophenyl]amino]carbonyl]-2,6- difluorobenzamide (lUPAC nomenclature is 1 -[4-(2-chloro-a,a,a-trifluoro-p-tolyloxy)-2- fluorophenyl]-3-(2,6-difluorobenzoyl)urea), having the following formula la:

la

Flufenoxuron of formula la, its preparation and its pesticidally activity are known from the literature (cf. US 5874615 and US 4698365).

Chlorfenapyr of formula II, its preparation and its pesticidal activity are likewise known from the literature (cf. EP-A 376 279 and EP-A 375 907).

More preferably, the composition of the invention is a combination of the benzoylurea compound of formula la (flufenoxuron) with the compound of formula II (chlorfenapyr) in synergisti- cally effective amounts which will be referred as "composition A". The composition of the invention comprises a benzoylurea compound of formula I as component (1 ) and the compound of formula II as component (2) in synergistically effective amounts.

In general, "synergistically effective amounts" means that the component (1 ) and the component (2) and optionally more active pesticidal components are usually applied in a weight ratio wherein the combined insecticidal effect of two or more components is greater than the sum of the individual insecticidal effect of each of the compounds. The synergistically ratio of component (1 ):component (2) according to the present invention are from 1 :500 to 100:1 , preferably from 1 :50 to 10:1 , in particular from 5:1 to 1 :20.

Depending on the nature of the compounds employed the weight ratio of compound of formula I and compound of formula II can start from 100:1 to 1 :100, preferably from 20:1 to 1 :20, in particular from 10:1 to 1 :10.

More preferred ratios of component (1 ) to component (2) in synergistically effective amount are 2:5, 1 :2, 1 :1 .

A very preferred ratio of component (1 ) to component (2) in synergistically effective amount is 2:5.

When preparing the composition according to the present invention, it is preferred to employ the pure benzoylurea compound of formula I and chlofenapyr, to which optionally further pesticidal active compounds, also against harmful fungi or else herbicidal or growth-regulating active compounds or fertilizers can be added.

The composition comprising the compounds of formulae I and II according to the present invention or the simultaneous or successive use of the compounds of formulae I and II exhibit out- standing synergistical action against pests from the following orders:

insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Ascia monuste orseis, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Dione juno juno, 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, Or- gyia 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, Scrobi- palpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodop- tera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni , rachiplusia nu, plusia spp, plusia putnami, plusia festucae, plusia oricbalcea, plusia orichalcea, tuta absoluta, and Zeiraphera canadensis, beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Am- phimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aph- thona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blito- phaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrot- ica longicornis, Diabrotica semipunctata, Diabrotica 12-punctata, Diabrotica speciosa, Diabrot- ica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllot- reta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria, flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gam- biae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadri- maculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia pla- tura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophi- lus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma Iineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, liriomyza huidobrensis, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus ar- gentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simu- Hum vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa, thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp , Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Re- ticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Termes natalensis, and Coptotermes formosanus, cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta aus- tralasiae, and Blatta orientalis, true bugs (Hemiptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dys- dercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis , Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nas- turtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schnei- deri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia ar- gentifolii, bemisia tabaci, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persi- cae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dy- saphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoas- ca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum eu- phorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nila- parvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalo- siphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus, ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogono- myrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Doli- chovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepi- thema humile, crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Lo- custa migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Me- lanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca america- na, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus se- negalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Callipta- mus italicus, Chortoicetes terminifera, and Locustana pardalina, arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcop- tidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus mou- bata, Ornithodorus hermsi, Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini, Der- manyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus palli- dus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetra- nychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacifi- cus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa, ticks (Ixo- dida), e.g. Phipicephalus sanguineus, or mites, such as Mesostigmata, e.g. Ornithonyssus ba- coti and Dermanyssus gallinae, Prostigmata, e.g. Pymotes tritici, or Astigmata, e.g. Acarus siro, or further mites species such as Polygophagotarsoemus latus, Phyllocoptruta oleivora, Eutetra- nychus banksi, Aculops lycopersici, Tenuipalpus hevea, Eriophyes querreronis, fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Scutigera coleoptrata, millipedes (Diplopoda), e.g. Narceus spp.,

Earwigs (Dermaptera), e.g. forficula auricularia, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, plant parasitic nematodes such as root-knot nematodes, Meloidogyne arenaria, Meloidogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne java- nica and other Meloidogyne species; cyst nematodes, Globodera rostochiensis, Globodera pallida, Globodera tabacum and other Globodera species, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; seed gall nemato- des, Anguina funesta, Anguina tritici and other Anguina species; stem and foliar nematodes, Aphelenchoides besseyi, Aphelenchoides fragariae, Aphelenchoides ritzemabosi and other 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, and Mesocri- conema species; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, Dity- lenchus myceliophagus and other Ditylenchus species; awl nematodes, Dolichodorus species; spiral nematodes, Helicotylenchus dihystera, Helicotylenchus multicinctus and other Helicoty- lenchus species, Rotylenchus robustus and other Rotylenchus species; sheath nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; lance ne- matodes, Hoplolaimus columbus, Hoplolaimus galeatus and other Hoplolaimus species; false root-knot nematodes, Nacobbus aberrans and other Nacobbus species; needle nematodes, Longidorus elongates and other Longidorus species; pin nematodes, Paratylenchus species; lesion nematodes, Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus curvitatus, Pratylenchus goodeyi, Pratylencus neglectus, Pratylenchus penetrans, Pratylenchus scribneri, Pratylenchus vulnus, Pratylenchus zeae and other Pratylenchus species; Radinaphelenchus cocophilus and other Radinaphelenchus species; burrowing nematodes, Radopholus similis and other Radopholus species; reniform nematodes, Rotylenchulus reniformis and other Rotylen- chulus species; Scutellonema species; stubby root nematodes, Trichodorus primitivus and other Trichodorus species; Paratrichodorus minor and other Paratrichodorus species; stunt nematodes, Tylenchorhynchus daytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species and Merlinius species; nematodes, Tylenchulus semipenetrans and other Tylenchulus species; dagger nematodes, Xiphinema americanum, Xiphinema index, Xiphinema diversicaudatum and other Xiphinema species; and other plant parasitic nematode species.

In a very preferred embodiment, the insect is selected from foliar insect pests.

An embodiment of the invention relates to a method of combating or controlling foliar insects selected from the order Lepidoptera. Within this embodiment, preference is given to insects from the family of Noctuidae, in particurlar to insects selected from the group consisting of Alabama argillacea, Anticarsia gemmatalis, Heliothis virescens, Pseudoplusia includens and Spo- doptera frugiperda. Further preference is given to insects selected from the families consisting of Pieridae (in particular Ascia monuste orseis as target), Nymphalidae (in particular Dione juno juno as target), Gelechiidae (in particular Phthorimaea operculella and tuta absoluta as targets) and Plutellidae (in particular Plutella xylostella as target).

Further embodiment of the invention relates to a method of combating or controlling foliar insects selected from sucking insects, in particular from lygus bugs, aphids and whiteflies. Further embodiment of the invention relates to a method of combating or controlling foliar insects selected from the order Hemiptera.

Further embodiment of the invention relates to a method of combating or controlling foliar insects selected from planthoppers (Delphacidae) and leafhoppers (Deltocephalidae). Among the planthoppers, the smaller brown planthopper (Laodelphax striatellus), brown planthopper (Nila- parvata lugens) and white-backed rice planthopper (Sogatella furcifera) are preferred target insects. Among the leafhoppers, green rice leafhoppers (Nephotettix cincticeps, Nephotettix nigropictus and Nephotettix virescens) are preferred target insects. Further embodiment of the invention relates to a method of combating or controlling foliar insects selected from the order Diptera, more preferably from the families Tephritidae (in particular Ceratitis capitata as target) and Agromyzidae (in particular Liriomyza huidobrensis as target.

Further embodiment of the invention relates to a method of combating or controlling foliar insects selected from beetles from the order Coleoptera. Within this embodiment, preference is given to insects from the family Chrysomelidae, in particular Diabrotica speciosa as target. Further embodiment of the invention relates to a method of combating or controlling foliar insects selected from thrips from the order of Thysanoptera. Within this embodiment, preference is given to insects from the family Thripidae, in particular Thrips tabaci as target. Further embodiment of the invention relates to a method of combating or controlling foliar insects selected from true bugs from the order of Hemiptera. Within this embodiment, preference is given to insects from the families Aleyrodidae (in particular Bemisia tabaci as target) and Aph- ididae (in particular Brevicoryne brassicae as target). Further embodiment of the invention relates to a method of combating or controlling foliar insects selected from the order of Trombidiformes. Within this embodiment, preference is given to insects from the family Tenuipalpidae in particular Brevipalpus phoenicis as target.

Further embodiment of the invention relates to a method of combating or controlling mites se- lected from the order of Trombidiformes. Within this embodiment, preference is given to mites from the families Tetranychidae (in particular Tetranychus urticae and Panonychus ulmi as target), Tarsonemidae (in particular Polyphagotarsonemus latus as target). and Eriophyidae (in particular Phyllocoptruta oleivora as target).

The compositions according to the present invention are used to control said target pests and/or to protect the plants which include the agricultural plants, seeds, roots and/or the above-ground parts of field, forage, plantation, glasshouse, orchard or vineyard crops, ornamentals, plantation or forest trees and/or any other plant(s) of interest.

Particular embodiment of the invention relates to a method for treating and/or protecting plants from attack or infestation pests by insects, acarids or nematodes comprising applying the compositions according to the present invention to plant, or soil or water in which the plant is growing. Preferably, the compositions are applied to agricultural plants.

The term "agricultural plants" is to be understood as plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibres (e.g. cotton, linen), chemical processes (oil, sugar), combustibles (e.g. wood, bio ethanol, biodiesel, biomass) or other chemical compounds. Agricultural plants may also include horticultural plants, i.e. plants grown in gardens (and not on fields), such as certain fruits, vegetables and flowers (e.g. rose). Preferred agricultural plants are for example cereals, e.g. wheat, rye, barley, triticale, oats, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, melon, watermelon, papaya, passion fruits, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as drybeans, lentils, peas, alfalfa or soybeans; oil plants, such as rape, oil-seed rape, canola, linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fibre plants, such as cotton, flax, hemp or jute; fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, toma- toes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, canola (oils seed rape), sugar cane or oil palm, corn, tobacco, nuts, coffee, tea, bananas, vines such as table grapes, grape juice grape vines or pepper, hop, turf, natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens (e.g. conifers) and on the plant propagation material, such as seeds, and the crop material of these plants.

In the context of the present invention, the term "plant" refers to an entire plant, a part of the plant or the propagation material of the plant, such as the seed, the seed piece, the transplant, the seedling or the cutting.

Particular embodiment relates to the method of treating and/or protecting agricultural plants selected from fruit-bearing plants, potato, rice, cereales, soybeans, drybeans, cotton, vegetables, surgarcane and horticultural plants. Fruit bearing plants of the invention include the major types of fruit for example, berries such as grapes, blueberries; drupes such as peaches, cherries, olives, plums and walnuts; aggregate fruit such as blackberries and raspberries; multiple fruit such as pineapples, figs and mulberries; and accessory fruit such as apples, pears and strawberries, and citrus fruit such as oranges, grapefruit, kumquats, lemons, limes, tangerines, temples, citrange, tangelo, pomelo, and citron.

Plants treated with the composition according to the present invention 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.

Some of the composition according to the present invention 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 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.

In particular, the seeds can be of tuberous and corm vegetables, such as arracacha, arrowroot, artichoke, canna, cassava, carrot, chayote root, chufa, dasheen, ginger, leren, onion, potato, radish, tanier, turmeric, yam bean, true yam; leafy vegetables, such as amaranth, arugula, car- doon, celery, celtuce, chervil, chrysanthemum, cress, dandelion, dock, endive, fennel, kale, leek, lettuce, orach, parsley, purslane, radicchio, rhubarb, spinach, swiss chard, tampala, head and stem brassica, such as broccoli, brussels sprout, cabbage, cauliflower, cavalo broccolo, curly cale, kohlrabi; leafy brassica greens, such as broccoli raab, cabbage, collards, kale, mi- zuna, mustard greens, mustard spinach, rape greens; fruiting vegetables such as beans, chili, postharvest, eggplant, groundcherry, pepino, pea, pepper, tomatillo, tomato. It is preferred that the seed be broccoli, carrot, cabbage, especially Chinese cabbage, red cabbage, savoy cabbage, white cabbage, celery, cauliflower, kohlrabi and radish seeds. Preferred embodiment of the invention relates to a method for protecting or treating cotton from the pestsAlbama Argillacea or Tetranychus urticae comprising the application of the composition A to the cotton plant.

Preferred embodiment of the invention relates to a method for protecting or treating citrus fruits plants from the pests Brevipalpus phoenicis, Phyllocoptruta oleivora and Polyphagotarsonemus latus comprising the application of the composition A to the citrus fruits plant. Preferred embodiment of the invention relates to a method for protecting or treating coffee plants from the pest Brevipalpus phoenicis comprising the application of the composition A to the cotton plant.

Preferred embodiment of the invention relates to a method for protecting or treating apples plants from the pest Panonychus ulmi comprising the application of the composition A to the apple plant.

Preferred embodiment of the invention relates to a method for protecting or treating soybean plants from the pests Anticarsia gemmatalis, Pseudoplusia includens, Tetranychus urticae, and Polyphagotarsonemus latus comprising the application of the composition A to the soybean plant.

Preferred embodiment of the invention relates to a method for protecting or treating onion plants from the pest Thrips tabaci comprising the application of the composition A to the onion plant.

Preferred embodiment of the invention relates to a method for protecting or treating potato plants from the pests Diabrotica speciosa, Liriomyza huidobrensis, Phthorimaea operculella and Thrips tabaci, comprising the application of the composition A to the potato plant. Preferred embodiment of the invention relates to a method for protecting cabbage plants from pest such as Ascia monuste orseis, Liriomyza huidobrensis comprising the application of the composition A to the cabbage plant.

Preferred embodiment of the invention relates to a method for protecting or treating chrisante- mum plants from the pests Thrips tabaci and Tetranychus urticae, comprising the application of the composition A to the Chrisantemum plant.

Preferred embodiment of the invention relates to a method for protecting or treating drybean plants from the pests Diabrotica speciosa, Thrips tabaci, Tetranychus urticae and Bemisia tabaci, comprising the application of the composition A to the drybean plant.

Preferred embodiment of the invention relates to a method for protecting or treating papaya plants from the pest Polyphagotarsonemus latus, comprising the application of the composition A to the papaya plant. Preferred embodiment of the invention relates to a method for protecting or treating passion fruit plants from the pest Dione juno juno, comprising the application of the composition A to the passion fruit plant.

Preferred embodiment of the invention relates to a method for protecting or treating melon or watermelon plants from the pest Thrips tabaci, comprising the application of the composition A to the melon or watermelon plant. Preferred embodiment of the invention relates to a method for protecting or treating corn plants from the pest Spodoptera frugiperda comprising the application of the composition A to the corn plant.

Preferred embodiment of the invention relates to a method for protecting or treating pepper plants from the pest Diabrotica speciosa comprising the application of the composition A to the pepper plant.

Preferred embodiment of the invention relates to a method for protecting or treating rose plants from the pest Tetranychus urticae comprising the application of the composition A to the rose plant.

Preferred embodiment of the invention relates to a method for protecting or treating tomato plants from the pests Aculops lycopersici, Tetranychus urticae and Tuta absoluta, comprising the application of the composition A to the tomato plant.

For use according to the present invention, the composition or the combination of the active compounds I and II, can be converted into 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 compound according to the invention.

Preferred embodiment is a method which is a foliar application of the compositions according to the present invention. The term "foliar application" as used herein refers to the application of the compositions through spray equipment to plant foliage. The foliar applications are made to all stages after plant emergence.

The formulations are prepared in a known manner, for example by extending the active compounds with solvents and/or carriers, if desired using emulsifiers and dispersants.

Solvents/auxiliaries which are suitable are essentially:

water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used,

carriers such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, al- kylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristearylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated

polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.

Suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N- methylpyrrolidone and water.

Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate. Suitable preservatives are for example Dichlorophen und enzylalkoholhemiformal.

Seed Treatment formulations may additionally comprise binders and optionally colorants.

Binders can be added to improve the adhesion of the active materials on the seeds after treat- ment. Suitable binders are block copolymers EO/PO surfactants but also polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisoutylenes, 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.I. Pigment Red 1 12, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

Example of a gelling agent is carrageen (Satiagel^®).

Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compounds. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.

The following are examples of formulations: 1 . Products for dilution with water

For seed treatment purposes, such products may be applied to the seed diluted or undiluted. A) Water-soluble concentrates (SL, LS)

10 parts by weight of the active compounds are dissolved with 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound dissolves upon dilution with water. A formulation having an active compound content of 10% by weight is obtained in this manner.

B) Dispersible concentrates (DC)

20 parts by weight of the active compounds are dissolved in 70 parts by weight of

cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion. The active compound content is 20% by weight.

C) Emulsifiable concentrates (EC)

15 parts by weight of the active compounds are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The formulation has an active compound content of 15% by weight. D) Emulsions (EW, EO, ES)

25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added into 30 parts by weight of water by means of an emulsifying machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The formulation has an active compound content of 25% by weight.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compounds are comminuted with addition of 10 parts by weight of dispersants and wetters and 70 parts by weight of water or an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound. The active compound content in the formulation is 20% by weight.

F) Water-dispersible granules and water-soluble granules (WG, SG)

50 parts by weight of the active compounds are ground finely with addition of 50 parts by weight of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound. The formulation has an active compound content of 50% by weight.

G) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)

75 parts by weight of the active compounds are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants and wetters as well as silica gel. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight.

H) Gel formulations (GF)

In a ball mill, 20 parts by weight of the active compounds, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or an organic solvent are ground to give a fine suspension. On dilution with water, a stable suspension having an active compound content of 20% by weight is obtained.

2. Products to be applied undiluted I) Dustable powders (DP, DS)

5 parts by weight of the active compounds are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having an active compound content of 5% by weight.

J) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compounds is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active compound content of 0.5% by weight.

K) ULV solutions (UL)

10 parts by weight of the active compounds are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted having an active compound content of 10% by weight.

For seed treatment, use is usually made of water-soluble concentrates (LS), suspensions (FS), dustable powders (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF). These formulations can be applied to the seed in undiluted form or, preferably, diluted. Application can be carried out prior to sowing.

In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1 -800 g/l of active ingredient, 1 -200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; the intention is to ensure in each case the finest possible distribution of the active compounds according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The active compounds concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %. The active compounds may also be used successfully in the ultra-low-volume process (ULV), by which it is possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives. Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the agents according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1. Compositions of this invention may also contain other active ingredients, for example other pesticides which may be insecticides, fungicides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. 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). These agents can be admixed with the mixtures according to the invention in a weight ratio of 1 :10 to 10:1. 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 compositions and methods according to the invention are particularly useful for the control of pests. The compositions and methods according to the present invention are particularly useful for combating animal pests.

The methods of controlling and/or combating animal pests comprise treating, that is to say contacting the animal pests with, their habitat, 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, the plants seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of a mixture of at least one active compound of formula / and at least the active compound of formula II. The pesticidal compositions according to the present invention are suitable for efficiently controlling invertebrate pests, particularly, insects, acarids and nematodes. They can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.

The pests may be controlled by contacting the pest itself, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the inventive mixtures or of

compositions comprising the the active compounds I and II.

The term "locus" hereabove 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 compositions comprising the active compounds according to the invention 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 effec- tive amount can vary for the various mixtures/compositions used in the invention. A pesticidally effective amount of the mixtures/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.

Whenever used in the text, the term pesticidally effective amounts according to the present invention always referrs to a synergistically effective amount of the compounds I and II.

It will be appreciated from the above, that the compounds I and II can be applied simultaneously, that is jointly (e.g. in the same formulation) or separately (e.g. in different formulations, such as in kit form), or in succession. If there is a successive application, it will also be appreciated that the subsequently applied compounds I and II should be applied to a subject (e.g. the pest, plant or animal) within a time scale so as to achieve or optimize the above referred to advantageous synergistic effect. The compounds I and II are usually applied in a weight ratio of from 20:1 to 1 :50, especially from 10:1 to 1 :10, in particular between 1 :5 to 1 :1 , particularly preferably between 1 :5 and 1 :3, also preferably between 1 :3 and 1 :2, mainly in the ratio of 1 :5, or 1 :4, or 1 :3, or 2:5, or 1 :2, or 2:4, or 3:5, or 4:5, or 1 :1. A very particurlar weight ratio of compounds I and II is respectively approximatively 2:5.

Depending on the desired effect, the application rates of the mixtures according to the invention are from 1 to 2500 g/ha, preferably from 5 to 2000 g/ha, more preferably from 50 to 1500 g/ha, in particular from 50 to 750 g/ha, even more particularly from 5 to 500g/ha. The compositions according to the invention are also suitable for the protection of the seed and the seedlings' roots and shoots, against soil pests.

Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders WS or granules for slurry treatment, water soluble powders SS and emulsion ES. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter, at sowing or after sowing. Preferred are FS formulations.

In the treatment of seed, the application rates of the inventive mixture are generally from 0.1 to 10 kg per 100 kg of seeds, in particular from 1 g to 2 kg per 100 kg of seeds. The separate or joint application of the compounds I and II or of the mixtures of the compounds I and II is carried out by spraying or dusting the seeds, the seedlings, the plants or the soils before or after sowing of the plants or before or after emergence of the plants. The invention also relates to the propagation products of plants, and especially the seed comprising, that is, coated with and/or containing, a composition as defined above or a composition containing additionally to the compounds of formulae I and II, more active ingredients or a mixture of two or more compositions each providing one of the active ingredientsof formulae I and II. The seed comprises the inventive mixtures in an amount of from 0.1 g to 10 kg per 100 kg, preferably from 1 g to 5 kg per 100 kg, most preferably from 1 g to 2.5 kg per 100 kg of seed.

The inventive composition 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.

The compositions according to the present invention are prefrably effective through foliar contact for the protection of plants.

According to a further embodiment of the invention, the pesticidal compositions are employed via soil application. Soil application is especially favorable for use against ants, termites, flies, crickets, grubs, root weevils, root beetles or nematodes. According to another embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the inventive compositions 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. Suitable feeding stimulants are chosen, for example, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, crickets powder, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey, or from salts such as ammonium sulfate, ammonium carbonate or ammonium acetate. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.

Formulations of the pesticidal compositions according to the present invention as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitoes, locusts or cockroaches. Aerosol recipes are preferably composed of the active compounds I and II, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 250 C, dimethylfor- mamide, N-methylpyrrolidone, dimethyl sulphoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases. The oil spray formulations differ from the aerosol recipes in that no propellants are used.

The combinations of the compounds according to the present invention and their respective compositions comprising carriers can also be used in mosquito coils and fumigating coils, smoke cartridges, vaporizer plates, long-term vaporizers, or other heat-independent vaporizer systems.

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 fibers, fabric, knitgoods, non-wovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.

The compositions according to the invention 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). The compositions according to the present invention are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant control composition of the present invention is directly applied to the nest of the ants or to its surrounding or via bait contact.

The mixture of compounds I and II or the compositions according to the invention can also be applied preventively to places at which occurrence of the pests is expected.

In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of the composition with the active compounds in ranges from 0.0001 to 500 g per 100 m², prefera- bly from 0.001 to 20 g per 100 m².

Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of the composition of the active compounds per m² treated material, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of the composition with the active compounds. For use in bait compositions, the typical content of the composition with the active compounds I and II is from 0.0001 weight % to 15 weight %, desirably from 0.001 weight % to 5 weight % of active compounds. The composition used may also comprise other additives such as a solvent of the active materials, a flavoring agent, a preserving agent, a dye or a bitter agent. Its attrac- tiveness may also be enhanced by a special color, shape or texture.

For use in spray compositions, the content of the composition with the active compounds I and II is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.

For use in treating agricultural plants, the rate of application of the composition with the active compounds I and II according to the present invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.

It was also an object of the present invention to provide composition suitable for treating, controlling, preventing and protecting warm-blooded animals, including humans, and fish against infestation and infection by pests. Problems that may be encountered with pest control on or in animals and/or humans are similar to those described at the outset, namely the need for re- duced dosage rates, and/or enhanced spectrum of activity and/or combination of knock-down activity with prolonged control and/or resistance management.

This invention also provides a method for treating, controlling, preventing and protecting warmblooded animals, including humans, and fish against infestation and infection by pests of the orders Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera, and Diptera, which comprises orally, topically or parenterally administering or applying to said animals a pes- ticidally effective amount of mixtures according to the invention.

The invention also provides a process for the preparation of a composition for treating, control- ling, preventing or protecting a warm-blooded animal or a fish against infestation or infection by pests of the Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera, and Diptera orders which comprises a pesticidally effective amount of a mixture according to the invention. The above method is particularly useful for controlling and preventing infestations and infections in warm-blooded animals such as cattle, sheep, swine, camels, deer, horses, poultry, goats, dogs and cats as well as humans.

Infestations in warm-blooded animals and fish including, but not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas may be controlled, prevented or eliminated by the mixtures according to the invention. For oral administration to warm-blooded animals, the composition according to the 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 according to the invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the mixture.

Alternatively, the composition according to the invention may be administered to animals parenteral^, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The mixtures according to the invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compositions according to the invention may be formulated into an implant for subcutaneous administration. In addition the compositions according to the invention may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the composition.

The compositions according to the invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, spot-on and pour-on formulations. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the inventive compounds. In addition, the compositions according to the invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.

Accordingly, in a further aspect of the invention there is provided the use of a composition ac- cording to the invention in the preparation of a veterinary medicament, specifically an antipara- siticidal medicament.

The following experiments are intended to illustrate the synergistic effect of the compositions according to the invention. The following tests demonstrate the control efficacy of compositions of this invention on specific pests. However, the pest control protection afforded by the compositions of this invention is not limited to these species. In certain instances, compositions of this invention are found to exhibit synergistic effects against certain other important invertebrate pests.

Use Examples

The purpose of the following examples is to illustrate the compositions according to the invention and their insecticidal activity but is not intended to limit the invention these 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, between two mixing partners can be calculated using the Limpel's formula, often called Colby's formula (Richer, 1987; Colby, 1967; Limpel et al., 1962, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 20-22):

E = X+Y-XY/100

E = expected percentage mortality of the combination of compound I and II

X = percentage mortality of compound X as measured independently

Y = percentage mortality of compound Y as measured independently.

Synergism is evident when the percentage observed mortality for the combination is greater than the percentage expected mortality calculated by Limpel's formula. In other terms, when the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.

The analysis of synergism or antagonism between the compositions according to this invention was determined using Limpel's formula.

Field experiments and foliar application were carried out using the commercial active compounds. The compositions according to the present inventions were used as tank-mixed in the stated con- centration and applied in the field in finished application rate of 400 liter pro hectar. The results observed are as follows summarized:

1. Activity against the mite pest Brevipalpus phoenicis on coffee plants Experiments were realized on coffe plants and the percentage of mortality observed 10 days after application is represented by the observed efficacy. The results are as follows summarized:.

2. Activity against the mite pest Anticarsia gemmatalis on soybean plants

Experiments were realized on soybean plants and the percentage of mortality observed 7 days after application is represented by the observed efficacy. The results are as follows summarized: concentration expected

observed efficacy

Product Name (g/100L) efficacy

Flufenoxuron 7 65

Clorfenapyr 18 60

Flufenoxuron + Clorfenapyr 7+18 95 86 3. Activity against the leafworm pest Pseudoplusia includens on soybean plants Experiments were realized on soybean plants and the percentage of mortality observed 7 days after application is represented by the observed efficacy. The results are as follows summarized: concentration expected

observed efficacy

Product Name (g/100L) efficacy

Flufenoxuron 7 42

Clorfenapyr 18 45

Flufenoxuron + Clorfenapyr 7+18 80 68

Claims

Claims:

1 . A pesticidal composition comprising, as active components,

1 ) a benzoylurea compound of the formula I

wherein

R is halogen, Ci-C4 alkyl, C1-C4 alkoxy or C1-C4 alkylthio;

R¹ is hydrogen, halogen, Ci-C4 alkyl, C1-C4 alkoxy or C1-C4 alkylthio

R² is fluorine;

R³ is hydrogen, halogen, nitro, cyano, Ci-C4 alkyl or C1-C4 haloalkyi;

n is an integer of 0, 1 , 2 or 3;

R⁴ is halogen or OR⁵; and

R⁵ is C1-C4 haloalkyi, C3-C7 halocycloalkyi, phenyl which may be or not substituted with up to three groups independently selected from halogen, C1-C4 haloalkyi groups, cyano groups or nitro groups, 2-pyridyl which may be or not substituted with up to three groups independently selected from halogen atoms, C1-C4 haloalkyi groups, cyano groups or nitro groups;

or an agriculturally acceptable salt thereof; and

a compound of the formula II

or an agriculturally acceptable salt thereof; in synergistically effective amounts. The pesticidal composition according to claim 1 wherein the compound of formula I is Λ/-

[[[4-[2-chloro-4-(trifluoromethyl)phenoxy]-2-fluorophenyl]amino]carbonyl]-2,6- difluorobenzamide.

The pesticidal composition according to claim 1 or 2, comprising the compound of the formula I and the compound of the formula II in a weight ratio from 100:1 to 1 :100.

A process for preparing the pesticidal composition according to any one of claim 1 to 3, said process comprising the step of mixing a compound of formula I with a compound of formula II.

Use of the pesticidal composition as defined in any one of claims 1 to 4 for combating invertebrate pests.

A method for controlling invertebrate pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a plant, seed, soil, area, material or environment in which the pests are growing or may grow, or the material, plant, seeds, soils, surfaces or spaces to be protected from pest attack or infestation with a syn ergistically effective amount of a composition as defined in any one of the claims 1 to 3.

A method for treating and/or protecting plants from attack or infestation pests comprising contacting a plant, or soil or water in which the plant is growing, with a composition as de fined in any one of claims 1 to 3.

The method according to claim 7, wherein the plant is a crop plant selected from fruit- bearing plants, potato, rice, cereales, soybeans, drybeans, cotton, vegetables, coffee, surgarcane and horticultural plants.

A method according to any one of claims 6 to 8 wherein the composition comprising the compounds of formaulae I and II is applied as foliar application.

A method of protection of plant propagation material and/or the plant which grow therefrom, which method comprises treating the plant propagation material with a composition as defined in any one of claims 1 to 3.

The method according to any one of claim 6 to 10 wherein the composition as defined in any one of claims 1 to 3 is applied in an amount from 5 to 500 g per hectar for each individual compound.

12. The method according to any one of claims 6 to 1 1 wherein the compounds I and II as defined in any one of claims 1 to 3 are applied simultaneously, that is jointly or separately, or in succession.