WO2020207870A1

WO2020207870A1 - Pesticidal mixtures

Info

Publication number: WO2020207870A1
Application number: PCT/EP2020/059195
Authority: WO
Inventors: Robert Reinhard; Karsten Koerber; Markus Gewehr
Original assignee: Basf Se
Priority date: 2019-04-12
Filing date: 2020-04-01
Publication date: 2020-10-15
Also published as: AR119714A1

Abstract

The present invention relates to pesticidal mixtures comprising 1.) the compound of formula (I) or the tautomers, enantiomers, diastereomers, or salts thereof; and 2.) one or more pesticidally active compounds II selected from the group of 2A. insecticides: fipronil, permethrin, esfenvalerate, tefluthrin, etofenprox, thiamethoxam, imidacloprid, clothianidin, acetamiprid, thiacloprid, dinotefuran, nitenpyram, spinosad, spinetoram, abamectin, emamectin, chlorfenapyr, teflubenzuron, methoxyfenozide, indoxacarb, metaflumizone, spirodiclofen, spiromesifen, cyflumetofen, flubendiamide, chlorantraniliprole, cyantraniliprole, tetraniliprole, tetrachlorantraniliprole, cyclaniliprole, cyhalodiamide, broflanilide, oxazosulfyl, acynonapyr, fluazaindolizin, tioxazafen; 2B. fungicides: propiconazole, metconazole, flutriafol, mefentrifluconazole, triticonazole, epoxiconazole, fenpropimorph, spiroxamine, picoxystrobin, metyltetraprole, sedaxane, isopyrazam, benzovindiflupyr, fluindapyr, isoflucypram, inpyrfluxam, 2B.17: 2-(difluoromethyl)-N-(1,1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide, 2B.18: 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, mancozeb, cyprodinil, flutriafol, fenpicoxamid, florylpicoxamid, chlorothalonil, quinofumelin, fluazinam, 2B.27: N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine; wherein component 1) and component 2) are present in a weight ratio of from 500:1 to 1:500. The invention relates further to methods and use of these mixtures for combating and controlling insects, acarids or nematodes in and on plants, and for protecting such plants being infested with pests.

Description

Pesticidal mixtures

The present invention relates to pesticidal mixtures of active ingredients having synergistically enhanced action and to methods of applying said mixtures.

The present invention relates to pesticidal mixtures comprising as active compounds 1.) the compound of formula (I)

or the tautomers, enantiomers, diastereomers, or salts thereof;

and

2.) one or more pesticidally active compounds II selected from the group of

2A. insecticides

fipronil, permethrin, esfenvalerate, tefluthrin, etofenprox, thiamethoxam, imidacloprid, clothianidin, acetamiprid, thiacloprid, dinotefuran, nitenpyram, spinosad, spinetoram, abamectin, emamectin, chlorfenapyr, teflubenzuron, methoxyfenozide, indoxacarb, metaflumizone, spirodiclofen, spiromesifen,

cyflumetofen, flubendiamide, chlorantraniliprole, cyantraniliprole, tetraniliprole,

tetrachlorantraniliprole, cyclaniliprole, cyhalodiamide, broflanilide, oxazosulfyl, acynonapyr, fluazaindolizin, tioxazafen;

2B. fungicides

propiconazole, metconazole, flutriafol, mefentrifluconazole, triticonazole, epoxiconazole, fenpropimorph, spiroxamine, picoxystrobin, metyltetraprole, sedaxane, isopyrazam, benzovindiflupyr, fluindapyr, isoflucypram, inpyrfluxam, 2B.17: 2-(difluoromethyl)-N-(1 ,1- dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide, 2B.18: 2-(difluoromethyl)-N-(3-ethyl- 1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, mancozeb, cyprodinil, flutriafol, fenpicoxamid, florylpicoxamid, chlorothalonil, quinofumelin, fluazinam, 2B.27: N'-(2,5- dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine; wherein component 1) and component 2) are present in a weight ratio of from 500:1 to 1 :500.

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 toxico logical 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. There also exists the need for pest control agents that combine knock-down 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.

Furthermore, there is a desire for pesticide compounds or combination of compounds, which when applied improve plants, which may result in“plant health”,“vitality of plant propagation material” or“increased plant yield”.

It is therefore an object of the present invention to provide agricultural combinations, which solve one or more than one of the discussed problems as

- reducing the dosage rate,

- enhancing the spectrum of activity,

- combining knock-down activity with prolonged control,

- improving resistance management,

- Improved plant health;

- Improved vitality of plant propagation material, also termed seed vitality;

- Increased plant yield..

It was therefore an object of the present invention to provide pesticidal mixtures which solve at least one of the discussed problems.

It has been found that this object is in part or in whole achieved by the combination of active compounds as defined herein.

Moreover, the invention relates to

- a composition comprising the pesticidal mixture as defined herein and at least one inert liquid and/or solid acceptable carrier;

- 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;

- a method of protecting plants from attack or infestation by invertebrate pests, contacting a plant, a plant propagation material or soil or water in which the plant is growing, with a pesticidally effective amount of the pesticidal mixture as defined herein;

- a plant propagation material comprising the pesticidal mixture as defined herein in an

amount of from 0.1 g to 10 kg per 100 kg of seed;

- a method for protection of plant propagation material comprising contacting the plant

propagation material with the pesticidal mixture as defined herein in an amount of from 0.1 g to 10 kg per 100 kg of plant propagation material;

- 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 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 compound I 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 compound I and at least one specific compound B;

- a method for protecting animals against infestation or infection by parasites which

comprises administering to the animals a parasiti cally effective amount of the pesticidal mixture as defined herein;

- a method for treating animals infested or infected by parasites which comprises

administering to the animals a parasitically effective amount of the pesticidal mixture as defined herein to the animal in need thereof; and

- the use of the pesticidal mixture as defined herein for combating parasites in and on

animals.

The compound of formula (I), also named“compound I” in the following, is N-[[2-fluoro-4- [(2S,3S)-2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1- yl]phenyl]methyl]cyclopropanecarboxamide and is known from WO2016/180802.

The commercially available compounds II 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 2B.17 and 2B.18 and their pesticidal action are known from WO2015197530, WO2016097003, WO2016139189, WO2016096944, WO2016096849, WO2017220491 ,

WO2018046431. Compound 2B.27 is known from EP2865265.

As used herein, the term“mixture(s) of the present invention” or“mixture(s) according to the invention” refers to the mixtures comprising

- compound of formula (I), and

- one or more compound(s) II as defined above.

In one embodiment, the mixture according to the invention is a mixture comprising the compound of formula (I), and a compound II as defined above.

The compounds I and the compounds II are understood to include their salts, tautomers, stereoisomers, N-oxides, and stereoisomers.

Moreover, it has also been found that simultaneous, that is joint or separate, application of the compound of formula (I) and one or more active compounds II or successive application of the compound of formula (I) and one or more active compounds II allows enhanced control of pests or fungi (especially in case compound II is a fungicide), compared to the control rates that are possible with the individual compounds. The mixtures of the invention may be a physical mixture of compound I and the at least one compound II. Accordingly, the invention also provides a mixture comprising compound I and at least one compound II. However, the composition may also be any combination of compound I with at least one compound II, it not being required for compound I and II to be present together in the same formulation.

An example of a composition according to the invention or to be used according to the invention in which compound I and the at least one compound II are not present together in the same formulation is a combipack. In a combipack, two or more components of a combipack are packaged separately, i.e., not jointly pre-formulated. As such, combipacks include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition. One example is a two- component combipack. Accordingly, the invention also relates to a two-component combipack, comprising a first component which in turn comprises compound I, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary, and a second component which in turn comprises at least one compound II, a liquid or solid carrier and, if appropriate, at least one surfactant and/or at least one customary auxiliary. More details, e.g. as to suitable liquid and solid carriers, surfactants and customary auxiliaries are described below. The "combined" use of compound I "in combination with" at least one compound II on the one hand can be understood as using a physical mixture of compound I and at least one compound II. On the other hand, the combined use may also consist in using compound I and the at least one compound II separately, but within a sufficiently short time of one another so that the desired effect can take place. More detailed illustrations of the combined use can be found in the specifications below.

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

The term "N-oxide" relates to a form of compounds I or II in which at least one nitrogen atom is present in oxidized form (as NO).

Salts of compound I or compounds II are preferably agriculturally acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion.

Compound I and compound II are usually applied in a weight ratio of 1000:1 to 1 :1000, preferably from 55:1 to 1 :500,, preferably from 100:1 to 1 :100, in particular from 20:1 to 1 :20. Compound I and compound II may also be applied in a weight ratio of 500:1 to 1 :10, or 100:1 to 1 :10, or 50:1 to 1 :10, or 20:1 to 1 :10, or 10:1 to 1 :500, or 10:1 to 1 :100, or 10:1 to 50:1 , or 10:1 to 1 :20.

The compounds II are abbreviated as shown in the following table:

The present invention therefore relates to the following mixtures:

Each single mixture of the mixtures M-1 to M-66 represents a preferred embodiment of the invention.

In a preferred embodiment, the invention relates to a mixture selected from M-1 , M-3, M-5, M-6, M-7, M-9, M-10, M-1 1 , M-12, M-13, M-14, M-16, M-17, M-18, M-19, M-20, M-21 , M-28, M-29, M-30, M-31 , M-35, M-36, M-41 , M-43, M-46, M-47, M-49, M-54, M-55, M-56, M-57, M-58, M-61 , M-62, M-64 and M-66.

In a further preferred embodiment, the invention relates to a mixture selected from M-3, M-5, M- 6, M-18, M-19, M-29, M-30, M-36, M-43, M-47, M-54, M-55, M-56, M-57, M-64 and M-66.

In a further preferred embodiment, the invention relates to a mixture selected from M-9, M-10, M-11 , M-12, M-13 and M-14.

In a further preferred embodiment, the invention relates to a mixture selected from M-1 , M-9, M- 10, M-1 1 , M-12, M-13, M-14, M-16 and M-18.

In a further preferred embodiment, the invention relates to a mixture selected from M-1 , M-10, M-11 , M-12, M-16 and M-18. In a further preferred embodiment, the invention relates to a mixture selected from M-41 , M-43, M-46, M-47, M-49, M-54, M-55, M-62 and M-64.

In a further preferred embodiment, the invention relates to a mixture selected from M-1 , M-10, M-11 , M-12, M-16, M-18, M-41 , M-43, M-46, M-47, M-49, M-54, M-55, M-62 and M-64.

Formulations

The invention also relates to agrochemical compositions comprising an auxiliary and at least one mixture of the present invention.

An agrochemical composition comprises a pesticidally effective amount of a mixture of the present invention.

The mixtures can be converted into customary types of agrochemical compositions, e.g.

solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials e.g. seeds (e.g. GF). 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.

The compositions are prepared in a known manner, e.g. described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants,

compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers, and binders.

Suitable solvents and liquid carriers are water and organic solvents.

Suitable solid carriers or fillers are mineral earths.

Suitable surfactants are surface-active compounds, e.g. anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Surfactants are listed in McCutcheon’s, Vol.1 : Emulsifiers & Detergents, McCutcheon’s

Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates.

Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants.

Suitable cationic surfactants are quaternary surfactants.

The agrochemical compositions generally comprise between 0.01 and 95%, preferably be tween 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100%.

Various types of oils, wetters, adjuvants, or fertilizer may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 : 100 to 100: 1.

The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the

agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

Application methods

The mixtures are suitable for use in protecting crops, plants, plant propagation materials, e.g. seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, e.g. seeds, or soil or water, in which the plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of a mixture.

The mixtures are also suitable for use in combating or controlling animal pests. Therefore, the invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, e.g. seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a mixture.

The mixtures of the present invention are effective through both contact and ingestion to any and all developmental stages, such as egg, larva, pupa, and adult.

The mixtures are also suitable as fungicides effective against a broad spectrum of

phytopathogenic fungi, including soil-borne fungi, in particular from the classes of

Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes,

Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective. They can be used in crop protection as foliar fungicides, fungicides for seed dressing, and soil fungicides. Moreover, they are suitable for controlling harmful fungi which occur in wood or roots.

The mixtures can be applied as such or in form of compositions comprising them.

The application can be carried out both before and after the infestation of the crops, plants, plant propagation materials by the pests.

The term "contacting" includes both direct contact (applying the mixtures/compositions directly on the animal pest or plant) and indirect contact (applying the mixtures/compositions to the locus).

The term“animal pest” includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects.

The term“plant” includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g. sugar beet, or fodder beet; fruits, e.g. pomes, stone fruits, or soft fruits, e.g. apples, pears, plums, peaches, nectarines, almonds, cherries, papayas, strawberries, raspberries, blackberries or gooseberries; leguminous plants, e.g. beans, lentils, peas, alfalfa, or soybeans; oil plants, e.g. rapeseed (oilseed rape), turnip rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts, or soybeans; cucurbits, e.g. squashes, pumpkins, cucumber or melons; fiber plants, e.g. cotton, flax, hemp, or jute; citrus fruit, e.g. oranges, lemons, grapefruits or mandarins; vegetables, e.g. eggplant, spinach, lettuce (e.g. iceberg lettuce), chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, e.g. avocados, cinnamon, or camphor; energy and raw material plants, e.g. corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts;

pistachios; coffee; tea; bananas; vines; hop; sweet leaf (Stevia); natural rubber plants or ornamental and forestry plants, , shrubs, broad-leaved trees or evergreens, eucalyptus; turf; lawn; grass. Preferred plants include potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee, or sugar cane; fruits; vines; ornamentals; or vegetables, e.g. cucumbers, tomatoes, beans or squashes.

The term“seed” embraces seeds and plant propagules including true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots, and means preferably true seeds.

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

For use in treating crop plants, e.g. by foliar application, the rate of application of the active ingredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare.

The mixtures are also suitable for use against non-crop insect pests. For use against said non crop pests, mixtures can be used as bait composition, gel, general insect spray, aerosol, as ultra-low volume application and bed net (impregnated or surface applied).

The term“non-crop insect pest” refers to pests, which are particularly relevant for non-crop targets, e.g. ants, termites, wasps, flies, ticks, mosquitos, bed bugs, crickets, or cockroaches, such as Aedes aegypti, Musca domestica, Tribolium spp.; termites such as Reticulitermes flavipes, Coptotermes formosanus; roaches such as Blatella germanica, Periplaneta Americana; ants such as Solenopsis invicta, Linepithema humile, and Camponotus pennsylvanicus.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). For use in bait compositions, the typical content of active ingredient is from 0.001 wt% to 15 wt%, desirably from 0.001 wt% to 5% wt% of the mixture.

Pests

The mixtures of the present invention are especially suitable for efficiently combating animal pests e.g. arthropods, and nematodes including:

insects from the sub-order of Auchenorrhyncha, e.g. Amrasca biguttula, Empoasca spp., Nephotettix virescens, Sogatella furcifera, Mahanarva spp., Laodelphax striatellus, Nilaparvata lugens, Diaphorina citri;

Lepidoptera, e.g. Helicoverpa spp., Heliothis virescens, Lobesia botrana, Ostrinia nubilalis, Plutella xylostella, Pseudoplusia includens, Scirpophaga incertulas, Spodoptera spp.,

Trichoplusia ni, Tuta absoluta, Cnaphalocrocis medians, Cydia pomonella, Chilo suppressalis, Anticarsia gemmatalis, Agrotis ipsilon, Chrysodeixis includens;

True bugs, e.g. Lygus spp., Stink bugs such as Euschistus spp., Halyomorpha halys, Nezara viridula, Piezodorus guildinii, Dichelops furcatus;

Th rips, e.g. Frankliniella spp., Thrips spp., Dichromothrips corbettii;

Aphids, e.g. Acyrthosiphon pisum, Aphis spp., Myzus persicae, Rhopalosiphum spp.,

Schizaphis graminum, Megoura viciae;

Whiteflies, e.g. Trialeurodes vaporariorum, Bemisia spp.;

Coleoptera, e.g. Phyllotreta spp., Melanotus spp., Meligethes aeneus, Leptinotarsa

decimlineata, Ceutorhynchus spp., Diabrotica spp., Anthonomus grandis, Atomaha linearia, Agriotes spp., Epilachna spp.;

Flies, e.g. Delia spp., Ceratitis capitate, Bactrocera spp., Liriomyza spp.;

Coccoidea, e.g. Aonidiella aurantia, Ferrisia virgate;

Anthropods of class Arachnida (Mites), e.g. Penthaleus major, Tetranychus spp.;

Nematodes, e.g. Heterodera glycines, Meloidogyne sp., Pratylenchus spp., Caenorhabditis elegans.

The mixtures of the present invention, wherein compound II is a fungicide from group 2B, are suitable for controlling the following causal agents of fungal 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. porn), 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. fulvurrr. 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, cotton 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 liriodendrr. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) 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) punctata, F. mediterranea,

Phaeomoniella chlamydospora (formerly Phaeoacremonium chlamydosporum ),

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 E. graminearum or E. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), E. oxysporum on tomatoes, E. solani (f. sp. glycines now syn. E. virguliforme ) and E. tucumaniae and E. brasiliense each causing sudden death syndrome on soybeans, and E. 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. fujikuror. Bakanae disease);

Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grain- staining 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. phased!) (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 triticr. 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. tabacina) 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. viticoia\ 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. ramorurrr. 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: eyespot, 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, R. areola (teleomorph: Mycosphaerella areola) on cotton 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 xanthir. 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.

Biological tests

1. Tests for insecticidal activity

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 (zero- interaction). To quantify the degree of drug synergy, several models have been proposed, such as those based on the Highest single agent model (HAS, or Gaddum additivity) (Berenbaum, 1989), the Loewe additivity model (Loewe, 1953) and the Bliss independence model (Bliss, 1939).

In the present case, the two mixing partners are acting mutually non-exclusively active, i.e. the Bliss independence model seems to be most appropriate to describe the zero-interaction effect (Greco et al. , 1992), where y_Buss is the expected effect based on the single effects of compound yi and y2, respectively (1). yBLiss = yi + y2 - yiy2 1

A reference model is used, particularly useful for the analysis of matrix data from plate-based high throughput experiments (Yadav et al., 2015). The model is named zero interaction potency (ZIP), which overcomes many of the limitations of the existing models and is based on independent dose-response curves for each of the two mixing partners. By combining the advantages of both the Loewe and Bliss models, the ZIP model assumes that two non interacting drugs are expected to incur minimal changes in their dose-response curves. In the ZIP model (Yadav et al., 2015, Formula 16) the zero-interaction situation (yZIP) is defined following formula (2), where X1 and X2 are the doses of compound 1 and 2, ml and m2 are the doses that produces the midpoint effect also known as relative EC50 or IC50 of compound 1 and 2 and A1 and K2 (h > 0) are the shape parameters indicating the sigmoid property or slope of the curves for compound 1 and 2.

An average delta score is calculated from the expectation of ZIP (d) and observed values, for each dose combination in the matrix. This allows for a surface plot of delta scores, to visualize the interaction landscape for a drug combination, aiming to identify synergistic and antagonistic dose regions for further dose optimization in a validation screen. The delta score have a unit of percentage inhibition and are directly comparable within and between drug combinations.

Finally, the average of all dose combination delta scores in the matrix can be calculated. The average score in percent, is called“ZIP synergy score” for the ZIP model or“Bliss synergy score” for the Bliss model.

An R-script called“syngergyfinder” based on the model above was published by

He, L. et al. (2018). It can be also downloaded from Bioconductor.org:

http://bioconductor.orq/packaqes/release/bioc/html/svnergyfinder.html

The following tests demonstrate the control efficacy of compounds, mixtures or compositions of this invention on specific pests. 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.

The mixtures tested comprise compound I, which belongs to IRAC class 30, and another component, which belongs to a different mode of action (IRAC classes):

Compound (I) + abamectin (IRAC class 6): Test 1-2.1

Compound (I) + acetamiprid (IRAC class 4a): Test 1-3.1

Compound (I) + clothianidin (IRAC class 4a): Tests I-4.2, I-5.2

Compound (I) + fipronil (IRAC class 2b): Tests 1-1.1 , 1-4.1 , 1-5.1

Compound (I) + imidacloprid (IRAC class 4a): Test I-4.3

Compound (I) + spinosad (IRAC class 5): Test 1-1.2

The mixtures were prepared according to the following dilution ratios (Table 0):

Table 0. Dilution ratios for the mixtures tested

Test 1-1 : Yellow fever mosquito ( Aedes aegypti)

For evaluating control of yellow fever mosquito ( Aedes aegypti) the test unit consisted of 96- well-microtiter plates containing 200mI of tap water per well and 5-15 freshly hatched A. aegypti larvae.

The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5mI, using a custom built micro atomizer.

For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together. Mixture applications were replicated 4 times into 4 separate microtiter plates.

After application, microtiter plates were incubated at 28 + 1°C, 80 + 5 % RH for 2 days. Larval mortality was then visually assessed and given a score (0, 50, or 100% control effect).

Table 1-1.1. a Observed mortalities (in %) in Aedes aegypti : Mixtures of compound I and fipronil

Table 1-1.1.b Expected mortalities (in %) in Aedes aegypti - Bliss model

Table 1-1.1.c Synergy scores (in %), in Aedes aegypti - Bliss model

Table 1-1.1.d Expected mortalities (in %) in Aedes aegypti - ZIP model

Table 1-1.1.e Synergy scores (in %), in Aedes aegypti - ZIP model

Table 1-1.2. a Observed mortalities (in %) in Aedes aegypti : Mixtures of compound I and spinosad

Table 1-1.2. b Expected mortalities (in %) in Aedes aegypti - Bliss model

Table 1-1.2. c Synergy scores (in %), in Aedes aegypti - Bliss model

Table 1-1.2.1.d Expected mortalities (in %) in Aedes aegypti - ZIP model

Table 1-1.2. e Synergy scores (in %), in Aedes aegypti - ZIP model

Test I-2: Boll weevil (Anthonomus grandis)

For evaluating control of boll weevil ( Anthonomus grandis) the test unit consisted of 96-well- microtiter plates containing an insect diet and 5-10 A. grandis eggs.

The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 5mI, using a custom-built micro atomizer.

For experimental mixtures in these tests, identical volumes of both mixing partners at the desired concentrations respectively, were mixed together. Mixture applications were replicated 4 times into 4 separate microtiter plates.

After application, microtiter plates were incubated at 23 + 1°C, 50 + 5 % RH for 5 days. Both egg and larval mortality was then visually assessed and given a score (0, 50, or 100% control effect).

Table 1-2.1. a Observed mortalities (in %) in Anthonomus grandis: Mixtures of compound I and Abamectin

Table 1-2.1.b Expected mortalities (in %) in Anthonomus grandis - Bliss model

Table 1-2.1. c Synergy scores (in %), in Anthonomus grandis - Bliss model

Table 1-2.1. d Expected mortalities (in %) in Anthonomus grandis - ZIP model

Table 1-2.1. e Synergy scores (in %), in Anthonomus grandis - ZIP model

Test 1-3: Tobacco budworm ( Heliothis virescens)

For evaluating control of tobacco budworm ( Heliothis virescens) the test unit consisted of 96- well-microtiter plates containing an insect diet and 15-25 H. virescens eggs. The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 10mI, using a custom-built micro atomizer.

After application, microtiter plates were incubated at 28 + 1°C, 80 + 5 % RH for 5 days. Both, egg and larval mortality was then visually assessed and given a score (0, 50, or 100% control effect).

Table 1-3.1. a Observed mortalities (in %) in Heliothis virescens : Mixtures of compound I and acetamiprid

Table 1-3.1. b Expected mortalities (in %) in Heliothis virescens - Bliss model

Table 1-3.1.c Synergy scores (in %), in Heliothis virescens - Bliss model

Table 1-3.1. d Expected mortalities (in %) in Heliothis virescens - ZIP model

Table 1-3.1.e Synergy scores (in %), in Heliothis virescens - ZIP model

Test I-4: Vetch aphid ( Megoura viciae)

For evaluating control of vetch aphid ( Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks. The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the leaf disks at 2.5mI, using a custom-built micro atomizer. For experimental mixtures in these tests, identical volumes of both mixing partners at the desired concentrations respectively, were mixed together. Mixture applications were replicated 4 times into 4 separate microtiter plates. After application, the leaf disks were air-dried and 5 - 8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at 23 + 1 °C, 50 + 5 % RH for 5 days. Aphid mortality and fecundity was then visually assessed and given a score (0, 50, or 100% control effect).

Table 1-4.1. a Observed mortalities (in %) in Megoura viciae : Mixtures of compound I and fipronil

Table 1-4.1. b Expected mortalities (in %) in Megoura viciae - Bliss model

Table 1-4.1.c Synergy scores (in %), in Megoura viciae - Bliss model

Table 1-4.1. d Expected mortalities (in %) in Megoura viciae - ZIP model

Table 1-4.1.e Synergy scores (in %), in Megoura viciae - ZIP model

Table 1-4.2. a Observed mortalities (in %) in Megoura viciae : Mixtures of compound I and clothianidin

Table 1-4.2. b Expected mortalities (in %) in Megoura viciae - Bliss model

Table 1-4.2. c Synergy scores (in %), in Megoura viciae - Bliss model

Table 1-4.2. d Expected mortalities (in %) in Megoura viciae - ZIP model

Table 1-4.2. e Synergy scores (in %), in Megoura viciae - ZIP model

Table 1-4.3. a Observed mortalities (in %) in Megoura viciae : Mixtures of compound I and imidacloprid

Table 1-4.3. b Expected mortalities (in %) in Megoura viciae : - Bliss model

Table 1-4.3. c Synergy scores (in %), in Megoura viciae : - Bliss model

Table 1-4.3. d Expected mortalities (in %) in Megoura viciae : - ZIP model

Table 1-4.3. e Synergy scores (in %), in Megoura viciae : - ZIP model

Test 1-5: Green peach aphid ( Myzus persicae)

For evaluating control of green peach aphid ( Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.

The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were pipetted into the aphid diet, using a custom built pipetter.

After application, 5 - 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at 23 + 1 °C, 50 + 5 % RH for 3 days. Aphid mortality and fecundity was then visually assessed and given a score (0, 50, or 100% control effect). Table 1-5.1. a Observed mortalities (in %) in Myzus persicae : Mixtures of compound I and fipronil

Table 1-5.1. b Expected mortalities (in %) in Myzus persicae - Bliss model

Table 1-5.1. c Synergy scores (in %), in Myzus persicae - Bliss model

Table 1-5.1.d Expected mortalities (in %) in Myzus persicae - ZIP model

Table 1-5.1. e Synergy scores (in %), in Myzus persicae - ZIP model

Table l-5.2.a Observed mortalities (in %) in Myzus persicae : Mixtures of compound I and clothianidin

Table 1-5.2. b Expected mortalities (in %) in Myzus persicae - Bliss model

Table 1-5.2. c Synergy scores (in %), in Myzus persicae - Bliss model

Table 1-5.2. d Expected mortalities (in %) in Myzus persicae - ZIP model

Table 1-5.2. e Synergy scores (in %), in Myzus persicae - ZIP model

Test 6: Greenhouse Whitefly ( Trialeurodes vaporariorum)

For evaluating control of Greenhouse Whitefly ( Trialeurodes vaporariorum) the test unit consists of 96-well-microtiter plates containing a leaf disk of egg plant leaf disk with white fly eggs. The compounds or mixtures are formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the insect diet at 2.5mI, using a custom-built micro atomizer. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together. Mixture applications are replicated 4 times into 4 separate microtiter plates.

After application, microtiter plates are incubated at 23 + 1 °C, 65 + 5 % RH for 6 days. Mortality of hatched crawlers is then visually assessed and given a score (0, 50, or 100% control effect).

References:

Berenbaum, M., C. (1989). What is synergy. Pharmacol Rev 41 : 93-141

Loewe, S. (1953). The problem of synergism and antagonism of combined

drugs. Arzneimittelforschung 3: 285-290

Bliss, C., I. (1939). The toxicity of poisons applied jointly. Ann Appl Biol 26:

585-615

Yadav, B.; Wennerberg, K.; Aittokallio, T.; Tang, J. (2015). Computational Searching for drug synergy in complex dose-response landscapes using an interaction potency model. Structural Biotechnology Journal 13: 504-513

Greco, W. ; Unkelbach, H. -D.; Poch, G.; Suhnel, J.; Kundi, M.; Bodeker, W. (1992) Consensus on concepts and terminology for combined-action assessment: The Saariselka agreement. Archives of Complex Environmental Studies. 4: 65-69

He, L; Kulesskiy, E.; Saarela, J.; Turunen, L; Wennerberg, K.; Aittokallio, T.; Tang, J. (2018). Methods for High-Throughput Drug Combination Screening and Synergy Scoring. In von Stechow, L.(ed.), Cancer Systems Biology: Methods and Protocols, chapter 17, 351-398.

Springer New York.

2. Microtests for fungicidal activity

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

They were tested as described below. 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.

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.

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.

F.1. Activity against the grey mold Botrytis cinerea in the microtiterplate test (BOTRCI)

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.

Table F.1 :

F.2. Activity against rice blast Pyricularia oryzae in the microtiterplate test (PYRIOR)

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 Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine 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.

Table F.2:

F.3. Activity against leaf blotch on wheat caused by Septoria tritici (SEPTTR)

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 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. Table F.3:

F.4. Activity against early blight caused by Alternaria solani (ALTESO)

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 Alternaria solani 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.

Table F.4:

5. Activity against wheat leaf spots caused by Leptosphaeria nodorum (LEPTNO)

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 Leptosphaeha nodorum 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.

Table F.5:

Claims

Claims:

1. Pesticidal mixtures comprising as active compounds

1.) the compound of formula (I)

or the tautomers, enantiomers, diastereomers, or salts thereof;

and

2.) one or more pesticidally active compounds II selected from the group of

2A. insecticides

cyflumetofen, flubendiamide, chlorantraniliprole, cyantraniliprole, tetraniliprole, tetrachlorantraniliprole, cyclaniliprole, cyhalodiamide, broflanilide, oxazosulfyl, acynonapyr, fluazaindolizin, tioxazafen;

2B. fungicides

propiconazole, metconazole, flutriafol, mefentrifluconazole, triticonazole,

epoxiconazole, fenpropimorph, spiroxamine, picoxystrobin, metyltetraprole, sedaxane, isopyrazam, benzovindiflupyr, fluindapyr, isoflucypram, inpyrfluxam, 2B.17: 2- (difluoromethyl)-N-(1 ,1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide, 2B.18: 2- (difluoromethyl)-N-(3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, mancozeb, cyprodinil, flutriafol, fenpicoxamid, florylpicoxamid, chlorothalonil, quinofumelin, fluazinam, 2B.27: N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine; wherein component 1) and component 2) are present in a weight ratio of from 500:1 to 1 :500.

2. Mixtures according to claim 1 , wherein the mixture comprises one compound II.

3. Mixtures according to any of claims 1 to 2, wherein the ratio of the mixture partners is

between 100:1 to 1 :100, preferably 50:1 to 1 :50, or preferably 20:1 to 1 :20.

4. Mixtures according to any of claims 1 to 3, wherein the compound II is an insecticide from group 2A.

5. Mixtures according to claim 4, wherein the compound II is selected from the group of fipronil, permethrin, esfenvalerate, tefluthrin, etofenprox, thiamethoxam, imidacloprid, clothianidin, acetamiprid, thiacloprid, dinotefuran, spinosad, spinetoram, abamectin, emamectin, chlorfenapyr, teflubenzuron, , flubendiamide, chlorantraniliprole,

cyantraniliprole, tetraniliprole, broflanilide, and oxazosulfyl.

6. Mixtures according to claim 4, wherein the compound II is selected from the group of

fipronil, thiamethoxam, imidacloprid, clothianidin, acetamiprid, thiacloprid, dinotefuran, spinosad and abamectin.

7. Mixtures according to any of claims 1 to 3, wherein the compound II is a fungicide from group 2B.

8. Mixtures according to claim 7, wherein the compound II is selected from the group of

metconazole, mefentrifluconazole, fenpropimorph, spiroxamine, metyltetraprole, isoflucypram, inpyrfluxam, 2B.17: 2-(difluoromethyl)-N-(1 ,1-dimethyl-3-propyl-indan-4- yl)pyridine-3-carboxamide, 2B.18: 2-(difluoromethyl)-N-(3-ethyl-1 ,1-dimethyl-indan-4- yl)pyridine-3-carboxamide, mancozeb, fenpicoxamid, florylpicoxamid, quinofumelin and 2B.27: N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine.

9. Mixtures according to claim 7, wherein the compound II is selected from the group of

metconazole, mefentrifluconazole, fenpropimorph, spiroxamine, methyltetraprole, isoflucypram, inpyrfluxam, florylpicoxamid and quinofumelin.

10. A pesticidal composition, comprising a liquid or solid carrier and a mixture as defined in any of claims 1 to 9.

11. A method for combating or controlling invertebrate pests, which method comprises

contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of a pesticidal mixture according to any one of claims 1 to 9.

12. 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 9.

13. Plant propagation material comprising a pesticidal mixture according to any one of claims 1 to 9 in an amount of from 0.1 g to 10 kg per 100 kg of seed.

14. A method for protection of plant propagation material comprising contacting the plant

propagation material with a pesticidal mixture according to any one of claims 1 to 9 in an amount of from 0.1 g to 10 kg per 100 kg of plant propagation material.

15. The use of a pesticidal mixture according to any one of claims 1 to 9 for protecting growing plants or plant propagation material from attack or infestation by invertebrate pests.