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    • 专利摘要:
    An agent containing two or more insecticides is provided
    公开号:DK201300089U1
    申请号:DK201300089U
    申请日:2013-05-31
    公开日:2013-07-12
    发明作者:Andersen Tine
    申请人:Andersen Tine；
    IPC主号:
    专利说明:

    i iDK 2013 00089 U1
    The present invention relates to an arthropod pesticidal composition, for crop protection and for use in public health for treatment of animal and humans against harmful pests, comprising the compounds methoxyfenozide and one or more avermectins as active ingredients. The combination shows a synergistic effect in the control of harmful arthropod pests. The invention further relates to a method for the control of harmful arthropod pests, and to the use of the composition for that purpose. The term arthropod pests include insects, nematodes, and arachnids throughout the present patent application.
    Background
    The pesticidal active compound methoxyfenozide is a member of the family of diacylhydrazine pesticides and is known from United States patent no. US 5,344,958. Methoxyfenozide is an ecdysone agonist which causes cessation of feeding and premature lethal moult. Methoxyfenozide acts primarily by ingestion also with some contact and ovicidal activity. Methoxyfenozide is used for control of insects from the order of Lepidoptera.
    The avermectins are a group of macrocyclic lactone compounds produced by fermentation of Streptomyces avermitilis and mutations thereof. The individual avermectins, either naturally derived or prepared by synthetic means (e.g. Ivermectin), are usually mixtures of up to 8 major components designated as Aia, Aib A2a, A2b, Bia, B]b B2a, B2b in various ratios. For instance abamectin is a mixture of the two closely structurally related components designated Bia and Bib usually in a 80:20 ratio, whereas the active compound known as Aversectin C further comprises additional components in addition to those in abamectin. Avermectin compounds are, for example, known from United States patents nos. 3,950,360; US 4,310,519; US 4,378,353; US 5,288,710; US 4,427,663; US 4,199,569; US 5,015,630; US 5,089,480, US 5,981,500 and PCT publication no. WO 02/068442-A1. Avermectins are neurotransmitter inhibitors and exhibits DK 2013 00089 U1 2 translaminar movement, which acts by contact and stomach action. Avermectins are used to control several pests in a varied range of crops or in public health. Avermectins are used to control several pests from the classes of Insecta, Arachnida, and Nematoda.
    The structure of the avermectins can be illustrated by the general formula (1), which only serves an illustrative purpose:
    10 When X represents a double bond, the substituents Ri and R2 on the C-22 and C-23 positions are not present. Illustrative substituents in the above formula (1) are those where Y represents H or an optionally substituted sugar or aminosugar unit, Ri represents H, R2 represents H or hydroxy, R3 represents alkyl or cycloalkyl and R4 represents H or alkyl.
    15 3 3DK 2013 00089 U1
    Examples of avermectins falling within the general structure (1) are:
    Name Y -C22Ri-X-C23R2 R3 R4 Avermectin A3a H0v OCH3 -CH=CH- sec-Butyl ch3 CHg i ^ H Avermectin Aib H0v 0CH3 -CH=CH- iso-Propyl ch3 CHg i H Avermectin A2a H0v OCH3 -CH2-CHOH- sec-Butyl ch3 CH3 1 ^ H Avermectin A2b HOv 0CH3 -CH2-CHOH- iso-Propyl ch3 CH3 1 ^ H Avermectin B3a H%,„. 0CH3 4” ] -CH=CH- sec-Butyl H CH3 1 ^ H Avermectin Bib h°v 0CH3 4” ] -CH=CH- iso-Propyl H CH3 1 ^ H Avermectin B2a H0/v 0CH3 -CH2-CHOH- sec-Butyl H CH3 i ^ H Avermectin B2b H0V 0CH3 -CH2-CHOH- iso-Propyl H CH3 H
    4 4DK 2013 00089 U1
    Name Y -C22Ri-X-C23R2 r3 R4 Ivermectin Bia och3 ch3 0 i H -ch2-ch2- sec-Butyl H Ivermectin B2a och3 πον Λ ch3 H -ch2-ch2- iso-Propyl H Doramectin och3 ch3 0 1 H -CH=CH- Cyclohexyl H Emamectin B]a och3 H3C-"H/v ch3 0 i H -CH=CH- sec-Butyl H Emamectin Bib och3 H3C—NH,V chT H -CH=CH- iso-Propyl H Eprinomectin Bia och3 h3c—·< > ch3 0 i H -CH=CH- sec-Butyl H Eprinomectin Bib OCH3 h3c—'·< > ch3 C’i H -CH=CH- iso-Propyl H
    Another avermectin is Selamectin known ftom United States patent no. US 5,981,500. Yet another group of avermectins are those disclosed in US patent no. 6,933,260, which are derivatives of the avermectins Bi having an 5 aminosulfonyloxy substituent in the 4”-position as indicated above. Avermectin compounds wherein the substituent at the 5-position in the above formula (1) is a substituted oximino group or the keto group are also known. When 5 5DK 2013 00089 U1 appropriate, the avermectins also include various salt forms thereof, e.g. Emamectin as its benzoate salt.
    Mixtures of pest Control agents, e.g. plant protection products, have been proposed in the literature to Control e.g. inhibit or destroy arthropod pests. However, lower application doses of pesticides and greater control of pests are required for safer handling as well as for environmental protection. This is achievable by applying combinations of pesticides, which do not only generate an additive enhancement, but also a synergistic effect.
    It is impossible to predict if a combination of pesticides has a synergistic effect, and it is therefore of high importance to develop novel pesticidal combinations, which exhibit a synergistic effect. Surprisingly, it has now been found that the combination of methoxyfenozide and one or more avermectins exhibit a synergistic effect against arthropod pests.
    Description of the invention
    The present invention relates to an arthropod pesticidal composition, for crop protection or for use in public health for treatment of animal and humans against harmful pests, comprising an arthropodal effective amount of the combination of methoxyfenozide and an avermectin, and to a method of controlling pests with said combination. The term “an avermectin” is to be understood as to include one or more compounds from the group of avermectins. The invention further relates to a process for the preparation of the novel composition, and to the use thereof for crop protection. The invention also relates to plants including plant propagation material treated with the combination. The invention additionally relates to the treatment of animal and humans against harmful pests. The invention further relates to a method for controlling harmful pests comprising exposing said harmful pests to an effective amount of methoxyfenozide and an avermectin. In a preferred embodiment the harm ful pests are exposed to an effective amount of methoxyfenozide and an avermectin, wherein 6 6DK 2013 00089 U1 methoxyfenozide and an avermectin are present in a synergistically effective amount.
    Methoxyfenozide and an avermectin in combination have a synergistic effect that increases the activity Spectrum of both compounds from two points of view. On the one hånd, the concentrations of methoxyfenozide and an avermectin are reduced with no reduction in the activity of said compounds. On the other hånd, the combination also achieves a high degree of pest Control where the individual compounds are completely inactive at low concentrations. This feature permits on the one hånd a widening of the pest Spectrum against the controllable arthropod pests and, on the other hånd, an enhancement in operator and environmental safety.
    Accordingly, the invention relates to an arthropod pesticidal composition comprising a synergistically acting combination of the pesticidal active compound methoxyfenozide, and of one or more active compounds selected among the avermectins, either one or both being in in the free form or in the form of an agrochemically acceptable salt thereof,
    Examples of agrochemically acceptable salts are typically acid addition salts of inorganic and organic acids, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, malonic acid, toluenesulfonic acid or benzoic acid.
    Preferred compositions within the scope of this invention are those that contain methoxyfenozide in the free form as active ingredient.
    Among preferred avermectins are Abamectin, Aversectin C, Doramectin, Emamectin, Eprinomectin, Ivermectin, Selamectin and salts thereof, and 7 7DK 2013 00089 U1 especially selected among Abamectin, Aversectin C, Ivermectin and Emamectin-benzoate with Abamectin being the most preferred choice.
    In one aspect, the invention relates to an arthropod pesticidal composition for crop protection consisting of a synergistically acting combination of the pesticidal active compound methoxyfenozide and an avermectin.
    The term “consisting of’ or “consists of’ means compositions wherein the total sum of methoxyfenozide and one or more compound from the group of avermectins add up to 100% of the pesticidal active ingredients within the composition, i.e. no other pesticidal active ingredients are present.
    In another aspect, the composition consists of an effective amount of a combination of methoxyfenozide, in the ffee form or as a salt, and an avermectin in a weight ratio of methoxyfenozide: avermectin ranging from about 1:1 to about 500:1.
    An effective amount of methoxyfenozide and an avermectin is any amount that has the ability to Control harmful pests. In general, satisfactory results are obtained when employing from about 1 to about 500 g/ha, preferably 50 to about 200 g/ha of methoxyfenozide, and more preferably from about 65 to about 150 g/ha; and from about 0.1 to about 100 g/ha, preferably about 1 to about 60 g/ha of an avermectin, and more preferably from about 10 to about 25 g/ha. However, higher and in particular lower doses may also provide adequate control.
    The weight ratio of methoxyfenozide and an avermectin is preferably selected to provide a synergistic pesticidal action and such ratios can be determined by the skilied person using well known principles. In general, the weight ratio of methoxyfenozide:avermectin range from about 1:1 to about 500:1, preferably 1:1 to 50:1, and more preferably 1:1 to 1:15, and even more preferably 1:1 to 1:10. The weight ratio of methoxyfenozide:avermectin will depend on various 8 8DK 2013 00089 U1 factors such as the mode of application, the harmful pests to be controlled, the useful plant to be protected, the application time, etc.
    In another aspect, the invention relates to a method for controlling animal and 5 human arthropod pests by exposing said harmful pests to 0.01 to 800 mg pr. Kg of bodyweight, preferably 0.1 to 200 mg pr. Kg of bodyweight of methoxyfenozide and more preferably 1 to 50 mg pr. Kg of bodyweight, and 0.1 to 1000 mg pr. kg of bodyweight, preferably 1 to 500 mg pr. Kg of bodyweight of an avermectin.
    10
    The combination according to the invention is particularly suitable for controlling representatives of the orders Hemiptera, Lepidotera, Hymenoptera, Thysanoptera, Coleoptera, Diptera and the sub-class Acarina.
    These orders typically include: of the order Lepidoptera, for example Acleris 15 spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Brassolis sophorae, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., 20 Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diaphania nitidalis, Diatraea spp., Diparopsis castanea, Earias spp., Ecdytolopha aurantiana, Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula andalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera coffeella, 25 Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Neoleucinodes elegantis, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Phyllocnistis citrella, Pieris rapae, Pieris spp., Plutella xylostella, 30 Prays spp., Pseudaletia sequax, Pseudoplusia includes, Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., 9 9DK 2013 00089 U1
    Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta and Yponomeuta spp.; of the order Coleoptera, for example Agriotes spp., Anthonemus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopelites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Oryzaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp. of the order Orthoptera, for example Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea måderne, Locusta spp., Periplaneta spp. and Schistocerca spp. of the order Isoptera, for example Reticulitermes spp. ', of the order Psocoptera, for example Liposcelis spp.; of the order Anoplura, for example Haematopinus spp., Linagnathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; of the order Mallophaga, for example Damalinea spp. and Trichodectes spp. ', of the order Thysanoptera, for example Franklinielia spp., Hercinothrips spp., Taeniothrips spp., Thripspalmi, Thrips tabaci and Scirtothrips spp.·, of the order Heteroptera, for example Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp., and Triatoma spp.; of the order Hemiptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Cemplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosama lanigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratcria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., 10 10DK 2013 00089 U1
    Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citrv, of the order Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomoriumpharaonis, Neodiprion spp., Solencpsis spp. and Vespa spp.', of the order Diptera, for example Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oseinelia frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; of the order Siphonaptera, for example Ceratophyllus spp. and Xenopsylla cheopis', of the order Thysanura, for example Lepisma saccharina and of the subclass Acarina, for example Acarus siro, Aceria sheldoni, Aculops lycopersici, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobiapraetiosa, Calipitrimerus spp., Chlosyine lacinia saundersii, Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Oligonychus ilicis,
    Oly gony chus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsenemus spp. and Tetranychus spp.; Halotydeus destructor, Penthaleus spp.
    Within the scope of this invention it is possible to control in particular insects 1) of the order Lepidoptera, especially Adoxophyes spp., Alabama argillaceae, Anticarsia gemmatalis, Brassolis sophorae, Clysia ambiguella, Clysia pomonella, Crocidolomia binotalis, Cydia spp., Diaphania nitidalis, Earias spp., Ecdytolopha aurantiana, Heliothis spp., Leucoptera coffeella, Lobesia botrana, Neoleucinodes elegantis, 11 11DK 2013 00089 U1
    Ostrinia nubilalis, Phthorimaea operculella, Phyllocnistis citrella, Plutella xylostella, Pseudaletia sequax, Pseudoplusia includes, Sparganothis spp. and Spodoptera spp. Tuta absoluta', 2) of the order Coleoptera in particular the family Curculionidae, more particularly Anthonemus spp., more particularly still A. grandis, very particularly the family Chrysomelidae, most preferably Leptinotarsa decemlineata; 3) of the order Hemiptera in particular the family Aphididae, more particularly the genus Aphis and the genus Myzus, most particularly A. gossypii, or Myzus persicae', in particular the family Aleurodidae, preferably Aleurothrixus floccus and Bemisia tabaci; in particular family Psyllidae, more preferably Psylla spp., preferably Franklinielia spp., Thripspalmi and Thrips tabaci', of the subclass Acarina in particular the species Aculops lycopersici and the family Eriophyidae, Aculus schlechtendali, Chlosyine lacinia saundersii, Oligonychus ilicis, Phyllocoptruta oleivora Polyphagotarsonemus latus and Tetranychus spp., Halotydeus destructor, Penthaleus spp., Bryobia praetiosa.
    The mixture comprising methoxyfenozide and an avermectin may also be used as a nematode-antagonistic biocontrol agent wherein the pests to be controlled is selected among Arthrobotrys spp., Chaetomium spp., Hirsutella spp., Pasteuria spp., Pochonia spp., Pseudomonas spp., and Rhizobacteria.
    Preferably, the pests are selected among the group consisting of Hirsutella spp., Paecilomyces spp., Pasteuria spp., Pochonia spp., Pseudomonas spp., and Rhizobacteria. More preferably (I) is selected from the group consisting of Hirsutella rhossiliensis, Hirsutella minnesotensis, Pasteuria penetrans, Pasteuria thomei, Pasteuria nishizawae, Pseudomonas fluorescens and Rhizobacteria.
    With the novel arthropod pesticidal combination, it is possible to control in particular pests of the above mentioned type that occur in plants or, especially, in cultivated plants and omamentals, in horticulture and in forestry, or in parts of 12 12DK 2013 00089 U1 such plants such as finit, blossoms, leaves, stems, tubers or roots, while in some cases parts of plants that grow later can also be protected against these pests.
    The arthropod pesticidal combination of this invention can be used with advantage for pest control in asparagus, strawberries, mushroom, ornamentals, hops, forests trees, cereals, sweet com, maize, grasses, sorghum, rice, and tobacco; Brassicas such as broccoli, brussels sprouts, cauliflower, cabbage, cauliflower; Crucifers such as beets, radish, carrots, rape, mustard, marrows; Cucurbitaceae such as squash, cucumber, melons; Lesuminosae such as beans, lentiis, peas, soybeans, groundnuts, chick peas; Pastures such as clover, grasses, alfalfa; Solanaceae such as Potatoes, tomatoes, paprika, beil pepper, chilli, aubergine; Umbelliferae such as celeriac, knob celery, celery root; Lamiaceae such as lemon mint; Alliaceae such as onion and garlic; Stone fruits such as plums, peaches, nectarine, almonds, cherries, apricots, Pome fruit such as Apples and pears; Citrus such as oranges, lemons, grapefruit, mandarins, kumquats; Other Orchard crops such as Persimmon, figs, nuts, olives, avocados, mango and vines; Plantation crops such as bananas, coffee, sugar cane, tea, pepper, pineapple, coconut, castor oil plants, cocoa beans, cinnamon, camphor, rubber plants; Fibrous crops such as cotton, flax, hemp and jute; Cane fruit such as raspberries, blackberries; Bush fruit such as blackcurrant, gooseberries, redcurrants, white currants; Leafv vegetables such as lettuce, spinach, ruccola, radicchio; Asteraceae such as Sunflower; Pavaveraceae such as poppy.
    The invention additionally relates to the use of a combination of methoxyfenozide and an avermectin for the manufacture of a medicament for the control of pests on humans or animals or their environs, said medicament comprising a reduced amount of pesticide while maintaining a similar pesticidal effect by replacing a part of the amount of pesticide with a synergistic amount of the combination.
    Further Utilities of the arthropod pesticidal combination of this invention are a method of controlling harmful pests on humans and animals. The method comprises administrating to a human or an animal in need thereof a 13 13DK 2013 00089 U1 pharmaceutical or veterinary effective amount of the combination. Animals on which the composition can be applied includes productive animals, breeding animals, zoo animals, pets as well as laboratory and experimental animals, such as mice, rats, guinea-pigs, golden hamsters, dogs, cats, cattle, horses, sheep, pigs, goats, camels, water buffalo, donkeys, rabbits, fallow deer and reindeer, fiir-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks. The combination may also be applied to the environs for the animals which include farmyard structures, dairy sheds, stables, poultry sheds, pig sties, dog and cat kennels and houses where dogs and cats are kept. The combination is effective against animal and human pests such as fly larvae; lice; mosquitoes such as Anopheles spp., Aedes spp., Culex spp., Mansonia spp.; flies such as Musca spp.; bedbugs such as Cimex lectularius, C. hemipterus; fleas such as Xenopsulla spp., pul ex spp., Ctenocephalides spp.; coackroaches such as Blatella spp., Periplaneta spp.; triatomine bugs such as Triatoma spp., Panstrongylus spp., Rhodinius spp.; and ticks & mites such as Ixodes spp., Dermaceutor spp., Haemaphysalis spp., Hyalomma spp., Borrelia spp., Ornithodorus spp.
    Additional pesticides, different from methoxyfenozide and the avermectins, may also be added to the combination, preferably so selected that the additional pesticides do not interfere negatively, with the synergistic relationship between methoxyfenozide and the avermectins. The optional additional pesticides, preferably insecticides and acaricides, can advantageously be included for example to widen the Spectrum of action or to prevent the build-up of resistance. Suitable examples of such additional pesticides are e.g.: acephate, acrinathrin, alanycarb, albendazole, aldicarb, alphamethrin, amitraz, azadirachtin, azinphos, azocyclotin, Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap, bephenium, betacyfluthrin, bifenazate, bifenthrin, bistrifluron, BPMC, brofenprox, bromophos, brotianide, bufencarb, buprofezin, butamisole, butocarboxin, butylpyridaben, cadusafos, cambendazole, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, 14 14DK 2013 00089 U1 chloroethoxyfos, chlorfenapyr, chlorofenvinphos, chlorofluazuron, chloromephos, chlorpyrifos, chromafenozide, cis-resmethrin, clocythrin, clofentezine, clorsulon, closantel, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton, diamphenethide, dibromosalan, dichlorophen, difenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diethylcarbamazine, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton, edifenphos, epsiprantel, esfenvalerate, ethiofencarb, ethion, ethiprole, ethofenprox, ethoprophos, etoxazole, etrimphos, febantel, fenamiphos, fenbendazole, fenzaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, flonicamid, fluazuron, flubendazole, flucycloxuron, flucythrinate, flufenoxuron, llufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, gamma-cyhalothrin, haloxon, heptenophos, hexaflumuron, hexachlorophene, hexythiazox, imidacloprid, indoxacarb, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, lambda-cyhalothrin, levamisole, lufenuron, malathion, mebendazole, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, methyridine, metolcarb, monocrotophos, morantel, naled, netobimin, niclopholan, niclosamide, nitroxynil, omethoate, oxamyl, oxfendazole, oxibendazole, oxyclozanide, oxydemethon M, oxydeprofos, parathion A, parathion M, parbendazol, permethrin, phenothiazine, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos, praziquantel, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozin, pyrachlophos, pyrantel, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, rafoxanide, rynaxypyr, salithion, sebufos, silafluofen, spinosad, spinetoram, spirodiclofen, spiromesifen, spirotetratmat, sulfotep, sulprofos, tebufenozid, tebuIcnpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetra-chlorvinphos, tetramisole, thenium, thiabendazole, thiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thiophanate, thuringiensin, tralomethrin, 15 15DK 2013 00089 U1 triarathen, triazophos, triazuron, trichlorfon, triclabendazole, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, zetamethrin.
    The additional pesticides may also include one or more fungicides. The optional additional fungicides can advantageously be included for example to broaden the Spectrum of action. Suitable examples of such additional fungicides are e.g.
    A) azoles, in particular: bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole; prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid; benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole, hymexazole; B) strobilurins, in particular: azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, or methyl (2-chloro-5-[l-(3-methylbenzyloxy-imino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[l-(6-methylpyridin-2-yl-methoxyimino)ethyl]benzyl)carbamate, methyl 2-(ortho-((2,5-dimethylphe-nyloxymethylene)phenyl)-3-methoxyacrylate; C) carboxamides, in particular: carboxin, benalaxyl, boscalid, fenhexamid, flu- tolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, N-(4'-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4'-trifluoromethylbi- phenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4'-chloro-3'-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(3',4'-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-l-methylpyrazole-4-carboxamide, N-(3',4'-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-l-methylpyrazole-4-carboxamide, 3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide, dimethomorph, flumorph, flumetover, fluopicolide (picobenzamid), zoxamide, carpropamid, diclocymet, mandipropamid, N-(2-{4- 16 16DK 2013 00089 U1 [3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl }ethyl)-2-methanesulfonyl-amino-3-methylbutyramide, N-(2-{4-[3-(4-chlorophenyl)-prop-2-ynyloxy] -3-methoxyphenyl} ethyl)-2-ethanesulfonylamino-3-methyl-butyr amide; D) heterocylic compounds, in particular: fluazinam, pyrifenox, bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil, triforine, fenpiclonil, fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone, vinclozolin, famoxadone, fenamidone, octhilinone, probenazole, amisulbrom, anilazine, diclomezine, pyroquilon, proquinazid, tricyclazole, 5-chloro-7-(4-methylpiperidin-l-yl)-6-(2,4,6-trifluorophenyl)-[l,2,4]triazolo[l,5-a]pyrimidine, 2-butoxy-6-iodo-3-propylchromen-4-one, acibenzolar-S-methyl, captafol, captan, dazomet, folpet, fenoxanil, quinoxyfen, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl ] pyri dine; E) carbamates, in particular: mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram, benthiavalicarb, diethofencarb, iprovalicarb, flubenthiavalicarb, propamocarb, methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methyl- butyrylamino)propanoate; and F) other active compounds, selected from guanidines: dodine, iminoctadine, guazatine, antibiotics: kasugamycin, streptomycin, polyoxine, validamycin A; nitrophenyl derivates: binapacryl, dinocap, dinobuton; sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane; organometal compounds: fentin salts, such as fentin-acetate; organophosphorus compounds: edifenphos, iprobenfos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; organochlorine compounds: chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate-methyl, tolylfluanid; inorganic active compounds: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; others: cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone and spiroxamine; 17 17DK 2013 00089 U1
    Depending on the intended objectives and the prevailing circumstances, the arthropod pesticidal combination may be employed in any conventional form, for example, in the form of a twin pack, or ready-to-use solutions, emulsifiable concentrates, emulsions, dilute emulsions, suspensions, wettable powders, soluble powders, dispersible powders, dusts, granules, soluble granules, dispersible granules, microemulsions, microcapsule suspensions e.g. capsules comprising both active ingredients or present within separate capsules, and mixtures thereof such as a ZC, ZE or ZW formulation. Such compositions can be formulated using diluents and formulation techniques that are known in the art for individually formulating the pesticides. For example, the pesticides may be mixed together, optionally with other formulating ingredients.
    The active ingredients are used in compositions in pure form, methoxyfenozide or any additional actives being typically used in a specific particle size, or preferably together with at least one of the diluents customary in formulation technology.
    The compositions may contain a diluent, which may be added during the formulation process, after the formulation process (e.g. by the user - a farmer or custom applicator), or both. The term diluent includes all liquid and solid agriculturally acceptable material-including carriers, which may be added to the pesticides to bring them in a suitable application or commercial form and include solvents, emulsifiers, and dispersants. The solid carriers typically used for dusts, granules and dispersible powders are usually natural mineral fillers such as aluminium silicate, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, absorbent carbon black, chalk, silica, and clays such as kaolin and bentonite calcite, talcum, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, including pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are calcite or sand. In addition, innumerable 18 18DK 2013 00089 U1 granulated materials of inorganic or organic nature may be used, especially dolomite or pulverised plant residues.
    Suitable solvents are typically aromatic hydrocarbons or partially hydrogenated aromatic hydrocarbons, preferably the fractions of alkylbenzenes containing 8 to 12 carbon atoms, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons such as paraffins or cyclohexane; alcohols such as ethanol, propanal or butanol; glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, diethylene glycol or 2-methoxyethanol or 2-ethoxyethanol; ketones such as cyclohexanone, isophorone or diacetone alcohol; strongly polar solvents such as N-methylpyrrolid- 2-one, dimethyl sulfoxide or Ν,Ν-dimethylformamide; water; vegetable oils or epoxidised vegetable oils such as rape oil, castor oil, coconut oil, or soybean oil, and silicone oils.
    The compositions may also contain surfactants, protective colloids, thickeners, penetrating agents, stabilizers, sequestering agents, anti-caking agents, coloring agents, corrosion inhibitors, and dispersants such as lignosulfite waste liquors and methylcellulose.
    Suitable surfactants compounds are nonionic, cationic and for anionic surfactants or mixtures of surfactants having good emulsifying, stability, spreading, dispersibility, wetting, or other surface-modifying properties. The surfactants listed below shall be regarded merely as exemplary; many more surfactants customarily employed in formulation technology and suitable for use in the practice of the invention are described in the relevant literature.
    Nonionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable nonionic surfactants are water-soluble polyadducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 19 19DK 2013 00089 U1 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Representative examples of nonionic surfactants are nonylphenol polyethoxyethanols, polyethoxylated eastor oil, polyadducts of polypropylene and polyethylene oxide, tributylphenol polyethoxylate, polyethylene glycol and octylphenol polyethoxylate. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable nonionic surfactants.
    Cationic surfactants are preferably quatemary ammonium salts carrying, as N-substituent, at least one Cs-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates orethyl sulfates. Examples are stearyltrimethylammonium chloride and benzyl bis(2-chloroethyl)ethylammonium bromide.
    Suitable anionic surfactants may be water-soluble soaps as well as water-soluble synthetic surface-active compounds. Suitable soaps are the alkali metal salts, alkaline earth metal salts and unsubstituted or substituted ammonium salts of higher fatty acids (Cio -C22), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures, which can be obtained e.g. from coconut oil or tall oil. Further suitable soaps are also the fatty acid methyl taurin salts. More frequently, however, synthetic surfactants are used, preferably fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and usually contain a C8-C22 alkyl radical, which also includes the alkyl moiety of acyl radicals. Typical examples are the sodium or calcium salt of ligninsulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Typical examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium 20 20DK 2013 00089 U1 salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde.
    Corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids, are also 5 suitable.
    The composition will usually comprise 0.1 to 99%, preferably 0.1 to 95%, of a combination of methoxyfenozide and an avermectin, and 1 to 99.9%, preferably 5 to 99.9%, of at least one solid or liquid carrier; usually they will contain 0 to 10 50%, preferably 0.1 to 20%, of surfactants (in each case percentages are by weight). Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations having a substantially lower concentration of active ingredient. Particularly preferred formulations will be made up as follows: (throughout, percentages are by 15 weight):
    Emulsifiable concentrates: Combination of methoxyfenozide and 1 to 99%, preferably 60 to 90% avermectin: Surfactant: 1 to 30%, preferably 1 to 20% Solvent: 0 to 80%, preferably 0 to 35%
    Dusts: Combination of methoxyfenozide and 99.9 to 90%, preferably 99.9 to 99% avermectin: Solid carrier: 0.1 to 10%, preferably 0.1 to 5%
    Suspension concentrates: Combination of methoxyfenozide and avermectin: 5 to 75%, preferably 10 to 50% DK 2013 00089 U1 21
    Water: 94 to 24%, preferably 88 to 30%
    Surfactant: 1 to 40%, preferably 2 to 30% 22DK 2013 00089 U1
    Suspo-emulsion Combination of methoxyfenozide and 1 to 99%, preferably 10 to 50% avermectin: Surfactant: 1 to 30%, preferably 1 to 20% Solvent 1 to 80%, preferably 1 to 35%
    Wettable powders: Combination of methoxyfenozide and 0.1 to 90%, preferably 1 to 80% avermectin: Surfactant: 1 to 50%, preferably 1 to 15% Solid carrier: 1 to 95%, preferably 15 to 90%
    Granulates: Combination of methoxyfenozide and 0.1 to 90%, preferably 1 to 80% avermectin: Surfactant: 1 to 50%, preferably 1 to 15% Solid carrier: 1 to 95%, preferably 15 to 90%
    Suspension composition for seed treatment: Combination 0.1 to 90%, preferably 1 to 80% Surfactant: 1 to 40%, preferably 1 to 20% Solvent: 1 to 90%, preferably 1 to 50% Pigment 0 to 40%, preferably 1 to 20% Binder 0 to 60%, preferably 1 to 40%
    The compositions may additionally contain other additives known in the art of formulation chemistry, such as pigments, and thickeners. The composition may also contain further solid or liquid diluents such as stabilisere, e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil or 23 23DK 2013 00089 U1 soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other Chemical agents for obtaining special effects, typically including bactericides, fungicides, or herbicides.
    The compositions of this invention are prepared by a known process in the absence of diluents, typically by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a specific particle size, and in the presence of at least one diluent, for example by mixing and grinding the active ingredient or mixture of active ingredients with the diluent(s) and/or surfactant(s). The invention also relates to the preparation of the compositions.
    The composition may be applied in various combinations of the two active compounds. For example, they may be applied as a single "ready-mix" form, or in a combined spray mixture composed from separate formulations of the active compounds, e.g. a "tank-mix" form. Thus, to be used in combination, it is not necessary that the two pesticides are applied in a physically combined form, or even at the same time, i.e. the components may be applied in a separately and/or sequentially application, provided that the application of the second active compound occurs within a reasonable period of time from the application of the first active compound. The combination effect results as long as the two pesticides are present at the same time, regardless of when they were applied. The order of applying the individual actives, i.e. methoxyfenozide and one or more avermectin compounds, is not essential.
    It is possible to Control the arthropod pests by applying an effective amount of the combination to the water, the pests food supply, habitat, breeding grounds, or their loci.
    The treatment of plants and parts of plants according to the invention may be carried out directly or by action on their environment (e.g. soil application), 24 24DK 2013 00089 U1 habitat or storage area according to customary treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, brushing-on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multilayer coating.
    The composition may also be formulated for use in a method of controlling harmful pests on animals or humans. Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. Pour-on formulations are poured or sprayed onto limited areas of the skin. Gels are applied to or spread on the skin. The combination may also be administered such that methoxyfenozide is given to the animal orally e.g. as a tablet, and the avermectin compound is applied to the skin of the animal e.g as a solution.
    According to the invention, it is possible to treat and protect all plants including parts of plants against harm ful pests. Plants are to be understood as all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Parts of plants are to be understood as all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned are leaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubers and rhizomes. Parts of plants also include harvested plants and vegetative and generative plant propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds (including stored seeds). The compounds of the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the locus of plant establishment e.g. prior to sowing, or during sowing, or prior to planting plant propagation material. The invention relates also to these methods of treating plant propagation material and to the plant propagation material so treated. The composition can also be applied to water in which the plant is growing.
    A preferred method of application in the field of plant protection is application 25 25DK 2013 00089 U1 to the foliage of the plants (foliar application), the number of applications and the rate of application depend on the risk of infestation by the particular arthropod pests.
    Rates of application of the composition will vary according to prevailing conditions such as degree of infestation, weather conditions, crop species, method of application, and application timing. Compositions containing methoxyfenozide and an avermectin may be applied in the manner, in which they are formulated, as discussed above.
    The methods of applying the composition, i.e. the methods of controlling arthropod pests of the indicated type, typically spraying, atomising, dusting, coating, dressing, scattering or pouring, selected in accordance with the intended objectives and prevailing circumstances, and the use of the compositions for controlling pests of the indicated type, are further objects of the invention.
    Typical rates of application, of the combination of methoxyfenozide and an avermectin, are in the range from 0.1 to 100,000 ppm, preferably from 0.1 to 10,000 ppm of active ingredient. The rate of application may vary over a wide range, and will depend on the nature of soil, the type of application (foliar application, seed dressing, application to the seed furrow), the cultivated plant, the pests to be controlled, the prevailing climatic conditions, and other factors governed by the type of application, time of application and target crop. The rates of application per hectare will be from about 1 to about 500 g/ha, preferably 50 to about 200 g/ha of methoxyfenozide, and more preferably from about 65 to about 150 g/ha; and from about 0.1 to about 100 g/ha, preferably about 1 to about 60 g/ha of an avermectin, and more preferably from about 10 to about 25 g/ha.
    26 DK 2013 00089 U1
    Biological Examples A synergistic effect is always obtained whenever the activity of the combination methoxyfenozide and an avermectin is greater than the sum of activities of the individually applied compounds.
    In the Colby method, also referred to as the Limpels method, the action to be expected (E) for a given active ingredient combination obeys the so-called Colby formula. According to Colby, the expected (additive) action of active ingredients A+B using p+q ppm of active ingredient is: Y-X Ίοο" E= X + Y — where ppm=milligrams of active ingredient (=a.i.) per litre of spray mixture X = Percentage mortality, compared with untreated Controls after treatment with the active compound methoxyfenozide at a rate of application of p kg/hectare Y = Percentage mortality, compared with untreated Controls after treatment with the active compound an avermectin at a rate of application of q kg/hectare.
    E = the expected pesticidal activity (percentage mortality compared with untreated Controls) after treatment with methoxyfenozide and an avermectin at a rate of application of p+ q kg a.i./ha.
    If the action actually observed (O) is greater than the expected action (E), then the action of the combination is superadditive, i.e. there is a synergistic effect. For a more detailed description of the Colby formula, see Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide combination," Weeds, Vol. 15, pages 20-22; 1967; see also Limpel et al., and Proc. NEWCC 16: 48-53 (1962), all of which are herein incorporated by reference in their entirety. The synergism ratio (R) is calculated as the ratio between the theoretical values and observed values.
    DK 2013 00089 U1 27
    Results show the combinations as herein described provides a synergistic effect when applied on pests. In particular the combinations of methoxyfenozide with Abamectin, Aversectin C, Doramectin, Emamectin, Eprinomectin, Ivermectin, and Selamectin.
    5
    权利要求:
    Claims (3)
    [1] 28 28 1 5 2 10 3 4 15 5 20 6 7 25 8 DK 2013 00089 U1 A method for controlling harmful arthropod pests comprising the exposure of said harmful pests to an effective amount of a combination of methoxyfenozide and an avermectin. The method according to claim 1, wherein the harm ful pests are of the order Hemipera, Lepidotera, Thysanoptera, Coleoptera, or the subclass Acarina. The method according to any of the claims 1 and 2, comprising the employment of 1 to 500 g/ha of methoxyfenozide. The method according to any of the claims 1 and 2, comprising the employment of 0.1 to 100 g/ha of an avermectin. A method according to any of the previous claims comprising the exposure of the arthropod pests, their food supply, habitat, breeding grounds or their loci to an effective amount of methoxyfenozide and an avermectin. A method for protecting plants from attack or infestation by pests comprising the exposure of the plant, or the soil, or water in which the plant is growing with an effective amount of methoxyfenozide and an avermectin. A method for controlling animal and human arthropod pests by exposing said harmful pests to an effective amount of methoxyfenozide and an avermectin. A composition comprising an effective amount of a combination of methoxyfenozide, in the free form or as a salt, and an avermectin in a weight ratio of methoxyfenozide: an avermectin ranging from about 1:1 to about 500:1. 30 DK 2013 00089 U1 29
    [2] 9. A composition according to claim 8, which further comprises a combination of methoxyfenozide and an avermectin with one or more additional pesticidal compound. 5 10. A composition according to claim 8 and 9, wherein methoxyfenozide and an avermectin is present in a form selected among ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, soluble powders, granules, soluble granules, dispersible granules, micro-emulsions, microcapsule suspensions and mixtures thereof. 10
    [3] 11. A process for preparing a composition according to any of the claims 8 to 10, which comprise mixing methoxyfenozide and an avermectin with a diluent(s) and/or surfactant(s). 15
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    2013-10-11| UHB| Application (utility model) shelved due to non-payment|Effective date: 20130925 |
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    DKPA201300089|2013-05-31|
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