PESTICIDE MIXTURES CONTAINING A PYRAZOLE COMPOUND

Description

[0001] The invention thus relates to pesticidal mixtures comprising as active compounds 1) 1-[(1RS)-1,2-dimethylpropyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-1H-pyrazole-4-carboxamide of formula I (common name dimpropyridaz): and 2) at least one further compound B selected from B.1) Succinate dehydrogenase inhibitors selected from a) pydiflumetofen, b) pyrapropoyne, and c) isoflucypram; B.3) Inhibitors of complex III at Qi site being florylpicoxamid; B.5) 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile; wherein component 1) and component 2) are present in a weight ratio of from 1000:1 to 1:1000.

[0002] One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control. Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests or crop diseases.

[0003] 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 and harmful fungi 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.

[0004] Compound of formula I is known from WO 2012 / 143317. This compound is mentioned to be useful for combating invertebrate pests.

[0005] WO 2018 / 234478 discloses pesticidal mixtures of a pyrazole compound and insecticides.

[0006] WO2016 / 128261 discloses ternary mixtures of a pyrazole compound with a fungicide and an insecticide.

[0007] WO 2016 / 128240 discloses ternary mixtures of a pyrazole compound with at least tw further fungicides.

[0008] WO 2017 / 001252 discloses mixtures of a pyrazole compound with a triazole fungicide.

[0009] WO 2015 / 189080 discloses mixtures of an anthranilamide compound and a pyrazole compound.

[0010] WO 2016 / 128239 discloses mixtures of a pyrazole compound with at least one biopesticide, such as microbial pesticides.

[0011] EP3111763 Al relates to pesticidal compositions of a pyrazole compound and a triazole compound.

[0012] EP3329777 Al relates to pesticidal compositions of a tetrazole compound and another pesticide selected inter alia from dimpropyridaz.

[0013] WO 2013 / 189801 relates to mixtures of a pyrazole compound and another pesticidal compound.

[0014] WO 2018 / 041665 discloses methods of controlling pests in modified plants, e.g. genetically modified plants, by using dimpropyridaz.

[0015] WO 2012 / 143317 relates to pyrazole compounds such as dimpropyridaz.

[0016] It is therefore an object of the invention to provide pesticidal mixtures which solve at least one of the discussed problems as reducing the dosage rate, enhancing the spectrum of activity or combining knock-down activity with prolonged control or as to resistance management.

[0017] It has been found that at least one of these objectives is achieved by the combination of active compounds defined in the outset.

[0018] Moreover, it has also been found that simultaneous, that is joint or separate, application of dimpropyridaz and one or more active compounds B or successive application of dimpropyridaz and one or more active compounds B allows enhanced control of pests and / or harmful fungi compared to the control rates that are possible with the individual compounds.

[0019] Moreover, the invention relates to an agricultural composition comprising the pesticidal mixture as defined herein and at least one inert liquid and / or solid acceptable carrier; a method for controlling or combating invertebrate pests, comprising contacting said pest or its food supply, habitat, breeding grounds with a pesticidally effective amount of the pesticidal mixture as defined herein; the use of the pesticidal mixture as defined herein for protecting growing plants or plant propagation material from attack or infestation by invertebrate pests; a non-therapeutic method for controlling phytopathogenic harmful fungi, wherein the fungi, their habitat or the plants to be protected against fungal attack, the soil or seed are treated with an effective amount of the pesticidal mixture comprising dimpropyridaz and at least one specific compound B; a method for protecting plants from phytopathogenic harmful fungi, wherein the fungi, their habitat or the plants to be protected against fungal attack, the soil or seed are treated with an effective amount of the pesticidal mixture comprising dimpropyridaz and at least one specific compound B; and

[0020] The mixtures of the invention may be a physical mixture of dimpropyridaz and the at least one compound B. Accordingly, the invention also provides a mixture comprising dimpropyridaz and at least one compound B. However, the composition may also be any combination of dimpropyridaz with at least one compound B, it not being required for compound A and B to be present together in the same formulation.

[0021] The term "invertebrate pest" (also referred to as animal pests) as used herein encompasses animal populations, such as insects, arachnids and nematodes, which may attack plants, thereby causing substantial damage to the plants attacked.

[0022] The term "compound(s) according to the invention", or "compound of formula I" or "pyrazole compound A" comprises dimpropyridaz as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof.

[0023] Dimpropyridaz has one center of chirality; it is present as mixture of enantiomers. The invention provides both the pure enantiomers or diastereomers and their mixtures and the use according to the invention of the pure enantiomers of dimpropyridaz or its mixtures.

[0024] The commercially available further compounds B may be found in The Pesticide Manual, 17th Edition, British Crop Protection Council (2015) among other publications, and its online database https: / / www.bcpc.org / product / bcpc-online-pesticide-manual-latest-version. Compounds B1, B3 and B5, resp., and their fungicidal or pesticidal action are known from CN 1456054, WO2017008583, CN 1907024, WO2015197530, WO2016097003, WO2016139189, WO2016096944, WO2016096849, WO2017220491, WO2018046431, WO2016109257, WO2016122802, WO 2016187201, WO2018098216, WO2018098243, WO2018098245, WO 2014 / 60177, WO2013116251, WO 2015036379, WO13127704, WO2015 / 65922, WO 2011 / 80044, WO2012 / 146125, WO 2009115557, WO2012045798, WO2012 / 69652, EP2865265, and WO2016 / 180802, resp.

[0025] We have found that simultaneous, that is joint or separate, application of dimpropyridaz and at least one compound B or successive application of dimpropyridaz and at least one compound B allows better control of animal pests and / or harmful fungi than is possible with the individual compounds alone (synergistic mixtures).

[0026] Dimpropyridaz can be used as synergist for different fungicidal active compounds. By simultaneous, that is joint or separate, application of dimpropyridaz with at least one active compound B1, B3 or B5, the fungicidal activity is increased in a superadditive manner.

[0027] The remarks made below concerning preferred embodiments of the variables further are valid on their own as well as preferably in combination with each other concerning dimpropyridaz, where applicable, as well as concerning the uses and methods according to the invention and the mixtures of the invention.

[0028] Particular aspects of the invention are any one of pesticidal mixtures A, C, and E: Pesticidal mixture A comprises as active components 1) dimpropyridaz, and 2) Succinate dehydrogenase inhibitors as defined in the outset; wherein component 1) and component 2) are present in a total weight ratio of from 1000:1 to 1:1000, preferably 100:1 to 1:100, particularly 20:1 to 1:20. In the afore mentioned ratios one embodiment relates to ratios from 1:1 to excessive dimpropyridaz; in another embodiment the ratios are from 1:1 to excessive compound 2).

[0029] Preferred mixtures A are combinations of dimpropyridaz with a compound 2) selected from: pydiflumetofen, pyrapropoyne, and isoflucypram in the mixture ratios as mentioned above.

[0030] Pesticidal mixture C comprises as active components 1) dimpropyridaz, and 2) florylpicoxamid; wherein component 11) and component 2) are present in a total weight ratio of from 1000:1 to 1:1000, preferably 100:1 to 1:100, particularly 20:1 to 1:20. In the afore mentioned ratios one embodiment relates to ratios from 1:1 to excessive dimpropyridaz; in another embodiment the ratios are from 1:1 to excessive compound 2.

[0031] Pesticidal mixture E comprises as active components 1) dimpropyridaz, and 2) the DMI fungicide 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-tria-zol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile wherein component 1) and component 2) are present in a total weight ratio of from 1000:1 to 1:1000, preferably 100:1 to 1:100, particularly 20:1 to 1:20. In the afore mentioned ratios one embodiment relates to ratios from 1:1 to excessive dimpropyridaz; in another embodiment the ratios are from 1:1 to excessive compound 2.

[0032] Binary mixtures of dimpropyridaz and a compound B are one preferred embodiment of the invention.

[0033] The mixtures of the invention are particularly suitable for controlling Lepidoptera, Coleoptera, Diptera, Thysanoptera, and Hemiptera.

[0034] In particular the mixtures are useful for the control of Thysanoptera and Hemiptera, especially Hemiptera.

[0035] In a preferred embodiment the invention relates to the pesticidal mixtures A, C and E which are particularly suitable for controlling pests from the family of Pentatomidae and / or Cicadellidae and / or Aleyrodidae and / or Aphididae, which are typical pests on soybean plants.

[0036] In one preferred embodiment, the invention relates to the use or method comprising the application of the pesticidal mixtures as defined above, wherein the pests are selected from the group consisting of green stink bug (Acrosternum hilare), brown marmorated stink bug (Halyomorpha halys), redbanded stink bug (Piezodorus guildinii), neotropical brown stink bug (Euschistus heros), brown stink bug (Euschistus servus), kudzu bug (Megacopta cribraria), red-shouldered stink bug (Thyanta custator) and the dusky-brown stink bug (Euschistus tristigmus), the southern green stink bug (Nezara viridula), and combinations thereof.

[0037] In one embodiment the stinkbug target is Nezara viridula, Piezodorus spp., Acrosternum spp.. Euschistus and in particular Euchistus heros are the preferred targets. More preferably the pesticidal mixtures are used to control Pentatomidae including green stink bug (Acrosternum hilare), brown marmorated stink bug (Halyomorpha halys), redbanded stink bug (Piezodorus guildinii), neotropical brown stink bug (Euschistus heros), brown stink bug (Euschistus servus), and kudzu bug (Megacopta cribraria), red-shouldered stink bug (Thyanta custator), dusky-brown stink bug (Euschistus tristigmus), and southern green stink bug (Nezara viridula).

[0038] The pesticidal mixtures A, C and E are preferably used on Faboideae, in particular soybean, to control stinkbugs, e.g. Nezara spp. (e.g. Nezara viridula, Nezara antennata, Nezara hilaris), Piezodorus spp. (e.g. Piezodorus guildinii), Acrosternum spp.(e.g. Acrosternum hilare), Euchistus spp. (e.g. Euchistus heros, Euschistus servus), Halyomorpha halys, Megacopta cribaria, Plautia crossota, Riptortus clavatus, Rhopalus msculatus, Antestiopsis orbitalus, Dectes texanus, Dichelops spp. (e.g. Dichelops furcatus, Dichelops melacanthus), Eurygaster spp. (e.g. Eurygaster intergriceps, Eurygaster maurd), Oebalus spp. (e.g. Oebalus mexicana, Oebalus poecilus, Oebalus pugnase, Scotinophara spp. (e.g. Scotinophara lurida, Scotinophara coarctatd).

[0039] Preferred targets include Acrosternum hilare, Antestiopsis orbitalus, Dichelops furcatus, Dichelops melacanthus, Euchistus heros, Euschistus servus, Megacopta cribaria, Nezara viridula, Nezara hilare, Piezodorus guildinii, Halyomorpha halys.

[0040] Further Pentatomidae pests that can be controlled according to the invention are Eysarcoris, in particular Eysarcoris aeneus.

[0041] The mixtures are preferably used on Faboideae, in particular soybean, to control whiteflies, e.g. sweetpotato whitefly (Bemisia tabaci).

[0042] The mixtures are preferably used on Faboideae, in particular soybean, to control aphids, e.g. soybean aphid (Aphis glycines).

[0043] The mixtures are preferably used on Faboideae, in particular soybean, to control leafhoppers, e.g. potato leafhopper (Empoasca fabae).

[0044] The mixtures are preferably used on Faboideae, in particular soybean, to control leafhoppers, e.g. Lorito verde (small green pakeet) (Empoasca kraemeri).

[0045] The pesticidal mixtures A, C and E are preferably used to control lepidopterans (Lepidoptera), such as Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura; beetles (Coleoptera), such as Anthonomus grandis, Anthonomus pomorum, and thrips (Thysanoptera), such as Scirtothrips citri.

[0046] The mixtures of the invention and compositions thereof, resp., are particularly suitable for controlling the following plant diseases: Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauci or A. porri), oilseed rape (A. brassicicola or brassicae), sugar beets (A. tenuis), fruits (e.g. A. grandis), rice, soybeans, potatoes and tomatoes (e. g. A. solani, A. grandis or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat (e.,g. A. triticina); Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Aureobasidium zeae (syn. Kapatiella zeae) on corn; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages); B. squamosa or B. allii on onion family), oilseed rape, ornamentals (e.g. B eliptica), vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladobotryum (syn. Dactylium) spp. (e.g. C. mycophilum (formerly Dactylium dendroides, teleomorph: Nectria albertinii, Nectria rosella syn. Hypomyces rosellus) on mushrooms; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum), soybeans (e. g. C. truncatum or C. gloeosporioides), vegetables (e.g. C. lagenarium or C. capsici), fruits (e.g. C. acutatum), coffee (e.g. C. coffeanum or C. kahawae) and C. gloeosporioides on various crops; Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosel-linia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punc-tata, F. mediterranea, Phaeomoniella chlamydospora (formerly Phaeoacremonium chlamydo-sporum), Phaeoacremonium aleophilum and / or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, oilseed rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguliforme ) and F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals, potatoes and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (syn. Monilia spp.: bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Zymoseptoria tritici formerly Septoria tritici: Septoria blotch) on wheat or M. fijiensis (syn. Pseudocercospora fijiensis: black Sigatoka disease) and M. musicola on bananas, M. arachidicola (syn. M. arachidis or Cercospora arachidis), M. berkeleyi on peanuts, M. pisi on peas and M. brassiciola on brassicas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), oilseed rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacinai) and soybeans (e. g. P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (syn. Leptosphaeria biglobosa and L. maculans: root and stem rot) on oilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off) on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad-leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, oilseed rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits (e. g. P. leucotricha on apples) and curcurbits (P. xanthii); Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (syn. Oculimacula yallundae, O. acuformis: eye-spot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or ,rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenopeziza spp., e.g. P. brassicae on oilseed rape; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea: rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, oilseed rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum) and P. oligandrum on mushrooms; Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis and R. commune (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables (S. minor and S. sclerotiorum) and field crops, such as oilseed rape, sunflowers (e. g. S. sclerotiorum) and soybeans, S. rolfsii (syn. Athelia rolfsii) on soybeans, peanut, vegetables, corn, cereals and ornamentals; Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (syn. Zymoseptoria tritici, Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setosphaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana, syn. Ustilago reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (syn. Podosphaera xanthii: powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum, syn. Septoria nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Trichoderma harzianum on mushrooms; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli), sugar beets (e. g. U. betae or U. beticola) and on pulses (e.g. U. vignae, U. pisi, U. viciae-fabae and U. fabae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. longisporum on oilseed rape, V. dahliae on strawberries, oilseed rape, potatoes and tomatoes, and V. fungicola on mushrooms; Zymoseptoria tritici on cereals.

[0047] The mixtures of the invention can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.

[0048] The compositions are prepared in a known manner, such as described by Mollet and Grube-mann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

[0049] The mixtures of the invention are employed as such or in form of compositions by treating the insects, the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal or fungal attack with a pesticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.

[0050] The invention also includes a method of combating animal pests and harmful fungi which comprises contacting the fungi and / or animal pests, their habit, breeding ground, food supply, cultivated plants, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of a mixture according to the invention.

[0051] Dimpropyridaz and the one or more compound(s) B are applied in a weight ratio of from 1000:1 to 1:1000, preferably from 100:1 to 1:100, or from 20:1 to 1:20, in particular from 10:1 to 1:10.

[0052] In general, "pesticidally effective amount" means the amount of the inventive mixtures or of compositions comprising the mixtures needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various mixtures and / or compositions used in the invention. A pesticidally effective amount of the mixtures and / or compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.Examples

[0053] The invention is now illustrated in further details by the following examples.

[0054] Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds. The presence of a synergistic effect in terms of percent control or efficiacy, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 20-22): E = X + Y − XY 100

[0055] The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies.

[0056] An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing.

[0057] The expected efficacies of active compound mixtures were determined using Colby's formula [R.S. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacies.

[0058] The following tests can demonstrate the control efficacy of mixtures or compositions of this invention on specific fungi. However, the pest control protection afforded by the compounds, mixtures or compositions is not limited to these species. In certain instances, combinations of a compound of this invention with other invertebrate pest control compounds or agents are found to exhibit synergistic effects against certain important invertebrate pests and / or harmful fungi.

[0059] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.

[0060] The product oxathiapiproline was used as commercial finished formulation and diluted with water to the stated concentration of the active compound.1. Activity against the grey mold Botrytis cinerea in the microtiterplate test

[0061] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Active compound / active mixture Concentration (ppm) Mixture Observed efficacy Calculated efficacy (%) Synergism (%) Dimpropyridaz1-00.25-10.063-0Pydiflumetofen0.063-42Isoflucypram0.25-57Pyrapropoyne1-26Dimpropyridaz0.0631:1604218Pydiflumetofen0.063Dimpropyridaz0.254 : 1704327Pydiflumetofen0.063Dimpropyridaz0.251 : 1815724Isoflucypram0.25Dimpropyridaz14 : 1735716Isoflucypram0.25Dimpropyridaz0.0631 : 4785721Isoflucypram0.25Dimpropyridaz0.251 : 4452718Pyrapropoyne1 2. Activity against leaf blotch on wheat caused by Septoria tritici

[0062] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Active compound / active mixture Concentration (ppm) Mixture Observed efficacy Calculated efficacy (%) Synergism (%) Dimpropyridaz0.25-70.063-5Isoflucypram0.063-40Dimpropyridaz0.0631:1814338Isoflucypram0.063Dimpropyridaz0.254: 1744430Isoflucypram0.063 3. Activity against Cercospora sojina in the microtiter test

[0063] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Cercospora sojina in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Active compound / active mixture Concentration (ppm) Mixture Observed efficacy Calculated efficacy (%) Synergism (%) Dimpropyridaz63-230.25-0Florylpicoxamid16-610.25-6Dimpropyridaz0.251:129623Florylpicoxamid0.25Dimpropyridaz634 : 11007030Florylpicoxamid16 4. Activity against Colletotrichum orbiculare in the microtiterplate test

[0064] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Colletotricum orbiculare in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Active compound / active mixture Concentration (ppm) Mixture Observed efficacy Calculated efficacy (%) Synergism (%) Dimpropyridaz63-14Pydiflumetofen16-59Dimpropyridaz634 : 1966531Pydiflumetofen16 5. Activity against Rhynchosporium secalis in the microtiterplate test

[0065] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Rhynchosporium secalis in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Compound B.5 is 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile. Active compound / active mixture Concentration (ppm) Mixture Observed efficacy Calculated efficacy (%) Synergism (%) Dimpropyridaz63-12Compound B.5)63-70Dimpropyridaz631:1927418Compound B.5)63 6. Activity against Sclerotinia sclerotiorum in the microtiterplate test

[0066] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Sclerotinia sclerotiorum in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Active compound / active mixture Concentration (ppm) Mixture Observed efficacy Calculated efficacy (%) Synergism (%) Dimpropyridaz0.25-0Pyrapropoyne1-27Dimpropyridaz0.251 : 4482721Pyrapropoyne1

Claims

1. Pesticidal mixtures comprising as active components 1) 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide of formula I: and 2) at least one further compound B selected from B.1) Succinate dehydrogenase inhibitors selected from a) pydiflumetofen, b) pyrapropoyne, and c) isoflucypram; B.3) Inhibitors of complex III at Qi site being florylpicoxamid; and B.5) 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile; wherein component 1) and component 2) are present in a weight ratio of from 1000:1 to 1:1000.

2. The mixtures of claim 1, wherein component 1) and component 2) are present in a weight ratio of from 100:1 to 1:100.

3. The mixtures of claim 1 or 2, wherein component 1) and component 2) are present in a weight ratio of from 20:1 to 1:20.

4. The mixtures of claim 1 or 2, wherein component 1) and component 2) are present in a weight ratio of from 10:1 to 1:10.

5. The mixtures of any of claims 1 to 4 comprising one compound B.

6. The mixtures of any of claims 1 to 5 wherein component 2) is selected from compounds B.1 a) to B.1 c).

7. The mixtures of any of claims 1 to 5 wherein component 2) is selected from compound B.3.

8. The mixtures of any of claims 1 to 5 wherein component 2) is compound B.5)9. A non-therapeutic method for controlling phytopathogenic harmful fungi, wherein the fungi, their habitat, or the plants to be protected against fungal attack, the soil or seed are treated with an effective amount of a pesticidal mixture according to claim 6 or 8.

10. A method for protecting growing plants or plant propagation materials from attack or infestation by invertebrate pests, which method comprises contacting a plant, a plant propagation material or soil or water in which the plant is growing, with a pesticidally effective amount of a pesticidal mixture according to any one of claims 1 to 8.