EP4712773A1 - Pesticidal mixtures comprising a benzamide compound - Google Patents

Abstract

Pesticidal mixtures comprising as active compounds A) the benzamide compound of formula (I) and B) at least one further compound B selected from fipronil, lambda-cyhalothrin, bifenthrin, tefluthrin, alpha-cypermethrin, thiamethoxam, clothianidin, acetamiprid, imidacloprid, dinotefuran, sulfoxaflor, triflumezopyrim, spinosad, spinetoram, abamectin, indoxacarb; metaflumizone, spiropidion, spidoxamat, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, broflanilide; dimpropyridaz, afidopyropen, 1-[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile), 6-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazole); and difenoconazole, prothioconazole, flutriafol, ipconazole, tebuconazole, mefentrifluconazole, triticonazole, fluoxytioconazol, metyltetraprole, azoxystrobin, trifloxystrobin, pyraclostrobin, sedaxane, penflufen, fluopyram, fluxapyroxad, pydiflumetofen, isoflucypram, cyclobutrifluram, oxathiapiprolin, fluoxapriprolin, metalaxyl, picarbutrazox, fludioxonil, thiabendazole, thiram, thiophanat-methyl; methods and use of these mixtures for combating invertebrate pests such as insects, arachnids or nematodes in and on plants, and for protecting such plants being infested with pests, especially also for protecting plant propagation material as like seeds.

Description

Pesticidal mixtures comprising a benzamide compound

The invention relates to a pesticidal mixture comprising as active compounds a benzamide compound and at least one further pesticide. Furthermore, the invention relates to methods of applying said mixture.

The invention thus relates to pesticidal mixtures comprising as active compounds

A) the compound A which is the compound of formula I:

B) at least one further compound B selected from: insecticides from groups 1 to 11 :

1) M.2 GABA-gated chloride channel antagonists: fipronil;

2) M.3 pyrethroids: lambda-cyhalothrin, bifenthrin, tefluthrin, alpha-cypermethrin;

3) M.4 nAChR agonists: thiamethoxam, clothianidin, acetamiprid, imidacloprid, dinotefuran, sulfoxaflor, tri- flumezopyrim;

4) M.5: spinosyns: spinosad and spinetoram;

5) M.6 avermectins: abamectin;

7) M.22 Voltage-dependent sodium channel blocker: indoxacarb; metaflumizone;

8) M.23 Inhibitors of the of acetyl CoA carboxylase: spiropidion, spidoxamat;

9) M.28 Ryanodine receptor-modulators: chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole;

10) M.30: broflanilide;

11) M.UN: dimpropyridaz, afidopyropen, 1-[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5- ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile) , 6-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro- 7-methy l-[1 , 3] d ioxolo [4, 5-f] benzi mid azole) ; and fungicides from groups 12 to 15:

12) inhibitors of ergosterol-biosynthesis: difenoconazole, prothioconazole, flutriafol, ipconazole, tebucona- zole, mefentrifluconazole, triticonazole, fluoxytioconazol;

13) strobilurins: metyltetraprole, azoxystrobin, trifloxystrobin, pyraclostrobin;

14) SDHIs: sedaxane, penflufen, fluopyram, fluxapyroxad, pydiflumetofen, isoflucypram, cyclobutrifluram;

15) further classes: oxathiapiprolin, fluoxapriprolin, metalaxyl, picarbutrazox, fludioxonil, thiabendazole, thiram, thiophanat-methyl; wherein component A and component B are present in a weight ratio of from 1000: 1 to 1 : 1000. One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control. Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests.

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

WO2023058748 describes benzamide compounds of formula I. These compounds are mentioned to be useful for combating invertebrate pests.

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

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

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

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 or harmful pathogenic fungi, comprising contacting said pest or its food supply, habitat, breeding grounds with a pesti cidal ly effective amount of the pesticidal mixture as defined herein;

- a method of protecting plants from attack or infestation by invertebrate pests or harmful pathogenic fungi, contacting a plant, a plant propagation material or soil or water in which the plant is growing, with a pesticidal ly 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 or harmful pathogenic fungi;

- 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 A as defined herein and at least one specific compound B as defined herein;

- 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 A as defined herein and at least one specific compound B as defined herein;

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

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

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

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

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

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

The compound of formula I has a stereocenter and thus exists in stereoisomers.

In one embodiment, the compound of formula I is the following stereroisomer compound I*:

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

The commercially available further compounds B may be found in The Pesticide Manual, 18th Edition, British Crop Protection Council (2018) among other publications, and its online database https://www.bcpc.org/product/bcpc- online-pesticide-manual-latest-version.

Compounds M.UN.1 and M.UN.2 are known from WC2020013147.

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

The compound of formula I can be used as synergists for certain insecticidal and fungicidal active compounds. By simultaneous, that is joint or separate, application of the compound of formula I with at least one active compound B, the insecticidal activity is increased in a superadditive manner.

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

Preferred embodiments of the invention relate to pesticidal mixtures wherein component A and component B are present in a total weight ratio of from 1000:1 to 1 :1000, 500:1 to 1 :500, 250:1 to 1 :250, 100:1 to 1 :100, 50:1 to 1 :50, or 10:1 to 1:10.

Other preferred embodiments of the invention relate to pesticidal mixtures wherein component A and component B are present in a total weight ratio of from 20:1 to 1 :500, preferably 10:1 to 1 :100, more preferably 10:1 to 1 :50, more preferably 10:1 to 1 :25, particularly 10:1 to 1 :10. In one embodiment, the mixtures of the invention are mixtures of the compound of formula I with a component B) selected from the insecticides from groups 1 to 11 as listed above.

In one embodiment, the mixtures of the invention are mixtures of the compound of formula I with a component B) selected from compounds fipronil, lambda-cyhalothrin, bifenthrin, tefluthrin, alpha-cypermethrin, thiamethoxam, clothi- anidin, acetamiprid, imidacloprid, dinotefuran, sulfoxaflor, triflumezopyrim, spinosad, spinetoram, abamectin, indoxa- carb; metaflumizone, spiropidion, spidoxamat, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, broflanilide; dimpropyridaz, afidopyropen, M.UN.1 : 1-[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5- ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile), M.UN.2: 6-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro-7- methyl-[1,3]dioxolo[4,5-f]benzimidazole); and difenoconazole, prothioconazole, flutriafol, ipconazole, tebuconazole, mefentrifluconazole, triticonazole, fluoxytioconazol, metyltetraprole, azoxystrobin, trifloxystrobin, pyraclostrobin, sedaxane, penflufen, fluopyram, fluxapyroxad, pydiflumetofen, isoflucypram, cyclobutrifluram, oxathiapiprolin, fluoxapriprolin, metalaxyl, picarbutrazox, fludioxonil, thiabendazole, thiram, thiophanat-methyl.

In a preferred embodiment, the mixtures of the invention are mixtures of the compound of formula I with component B) selected from fipronil, lambda-cyhalothrin, bifenthrin, tefluthrin, alpha-cypermethrin, thiamethoxam, clothianidin, acetamiprid, imidacloprid, spinosad, spinetoram, abamectin, indoxacarb; spiropidion, spidoxamat, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, broflanilide; and dimpropyridaz.

In a more preferred embodiment, the mixtures of the invention are mixtures of the compound of formula I with component B) selected from lambda-cyhalothrin, bifenthrin, tefluthrin, alpha-cypermethrin, thiamethoxam, clothianidin, acetamiprid, spinosad, spinetoram, abamectin, indoxacarb; chlorantraniliprole, cyantraniliprole, broflanilide and dimpropyridaz.

In an even more preferred embodiment, the mixtures of the invention are mixtures of the compound of formula I with component B) selected from lambda-cyhalothrin, bifenthrin, tefluthrin, alpha-cypermethrin, clothianidin, spinosad, abamectin, chlorantraniliprole and broflanilide.

In particular, the mixture of the invention is a mixture selected from mixtures M-1 to M-21 :

In one embodiment, the mixture of the invention is a mixture selected from mixtures N-1 to N-54:

Preferred mixtures of the invention are the mixtures N-2 = M-2, N-3 = M-3, N-4 = M-4, N-5 = M-5, N-7 = M-7, N-13 = M-10, N-15 = M-12, N-20 = M-16, N-24 = M-20. In a particular embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) fipronil.

In a particular embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) M.3 pyrethroids selected from lambda-cyhalothrin, bifenthrin, tefluthrin and alpha-cypermethrin.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) lambda-cyhalothrin.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) bifenthrin.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) tefluthrin.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) alpha-cypermethrin

In a particular embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) M.4 nAChR agonists selected from: thiamethoxam, clothianidin, acetam- iprid, imidacloprid, dinotefuran, sulfoxaflor and triflumezopyrim;

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) M.4 nAChR agonists selected from: thiamethoxam, clothianidin, ac- etamiprid, imidacloprid.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) thiamethoxam.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) clothianidin.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) acetamiprid,

In one embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) imidacloprid.

In a particular embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) M.5: spinosyns selected from spinosad and spinetoram;

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) spinosad.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) spinetoram.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) abamectin.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) indoxacarb. In one embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) M.23 Inhibitors of the of acetyl CoA carboxylase selected from spiropidion and spidoxamat.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) spiropidion.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) spidoxamat.

In a particular embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) a M.28 Ryanodine receptor-modulators selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole and tetraniliprole.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) chlorantraniliprole.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) cyantraniliprole.

In one embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) cyclaniliprole.

In one embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) tetraniliprole.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) broflanilide.

In one preferred embodiment of the invention, the mixtures of the invention comprise as active components A) the compound of formula I as defined above, and B) dimpropyridaz.

In a preferred embodiment, the mixtures of the invention are mixtures of the compound of formula I with component B) selected from prothioconazole, tebuconazole, cyclobutrifluram, oxathiapiprolin and fludioxonil.

Binary mixtures of the compound of formula I and one compound B are one preferred embodiment of the invention.

The invention also relates to agrochemical compositions comprising an auxiliary and a mixture of the invention. An agrochemical composition comprises a pesticidally effective amount of a mixture of the invention.

The compound I and its mixtures can be converted into customary types of agro-chemical compositions, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, CD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EC, 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 Mono- graph No. 2, 6th Ed. May 2008, CropLife International. The compositions are prepared in a known manner, e.g. described by Mol let 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 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 qua-ternary surfactants.

The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 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 agro-chemical 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.

The mixtures of the invention 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 pesticidal ly effective amount of a mixture of the invention.

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

The mixtures of the invention 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 compounds/compositions directly on the animal pest or plant) and indirect contact (applying the compounds/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 I 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, grape-fruits 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 compounds/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 of the invention are also suitable for use against non-crop insect pests. For use against said non-crop pests, the mixture of the invention can be used as bait composition, gel, general insect spray, aero-sol, as ultra-low volume application and bed net (impregnated or surface applied). The mixtures of the 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, Mahanarva fimbriolata, Nilaparvata lugens, Diaphorina ci tri;

Lepidoptera, e.g. Diatraea saccharalis, Helicoverpa spp., Heliothis virescens, Lobesia botrana, Manduca sexta, Os- trinia nubilalis, Plutella xylostella, Pseudoplusia includens, Scirpophaga incertulas, Sesamia sp., Spodoptera spp., Trichoplusia ni, Tuta absoluta, Cnaphalocrocis medialis, 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;

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

Aphids, e.g. Acyrthosiphon pisum, Aphis spp., Myzus persicae, Macrosiphum euphorbiae, Rhopalosiphum spp., Schizaphis graminum, Megoura viciae;

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

Coleoptera, e.g. Atomaria linearia, Phyllotreta spp., Melanotus spp., Meligethes aeneus, Leptinotarsa decimlineata, Ceutorhynchus spp., Diabrotica spp., Anthonomus grandis, Atomaria linearia, Agriotes spp., Epilachna spp.; Hypoth- enemus hampei; Lissorhoptrus oryzophilus; Melanotus spp.; Otiorhynchus sulcatus; Oulema spp.; Phyllotreta spp.; Popillia japonica; Psylliodes chrysocephala;

Flies, e.g. Delia spp., Ceratitis capitata, Bactrocera spp., Liriomyza spp.; Mayetiola destructor; Rhagoletis spp. Coccoidea, e.g. Aonidiella aurantia, Ferrisia virgate; Coccus spp.; Quadraspidiotus preniciosus Anthropods of class Arachnida (Mites), e.g. Penthaleus major, Panonychus spp.; Tetranychus spp.;

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

The mixtures of the invention 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 imperfect!) . They can be used in crop protection as foliar fungicides, fungicides for seed dressing, and soil fungicides. The compounds I and the compositions thereof are preferably useful in the control of phytopathogenic fungi on various plants, as described herein.

The mixtures of the invention are particularly suitable for controlling the following causal agents of plant diseases: Albugo spp. (white rust) on ornamentals, vegetables (e.g. A. Candida) and sunflowers (e.g. A. tragopogonis),' Alter- naria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauci or A. pom), 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 (8. zeicola) on corn, e.g. spot blotch (8. sorokin- iana) on cereals and e.g. 8. 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); 8. squamosa or 8. allii on onion family), oilseed rape, ornamentals (e.g. 8 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: 8. 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. linde- muthianum), 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 lirio- dendri: 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-re- pentis: 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. pyn), 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; Grainstain- ing 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. 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. tetra- spora) 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, 0. 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; Pseu- dopezicula 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 tiit- ici, 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. Us- tilago 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. Phaeo- sphaeria] 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 ele- gans),' 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. inaegualis) 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. fungi- cola on mushrooms; Zymoseptoria tritici on cereals.

The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases: rusts on soybean and cereals (e.g. Phakopsora pachyrhizi and P. meibomiae on soy; Puc- cinia tritici and P. striiformis on wheat); molds on specialty crops, soybean, oil seed rape and sunflowers (e.g. Botrytis cinerea on strawberries and vines, Sclerotinia sclerotiorum, S. minor and S. rolfsii on oil seed rape, sunflowers and soybean); Fusarium diseases on cereals (e.g. Fusarium culmorum and F. graminearum on wheat); downy mildews on specialty crops (e.g. Plasmopara viticola on vines, Phytophthora infestans on potatoes); powdery mildews on specialty crops and cereals (e.g. Uncinula necator on vines, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals); and leaf spots on cereals, soybean and corn (e.g. Septoria tritici and S. nodorum on cereals, S. glycines on soybean, Cercospora spp. on corn and soybean).

The mixtures of the invention are particularly useful in seed treatment and soil treatment.

The term "seed treatment” comprises e.g. seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods. Preferably, the seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants. The invention also comprises seeds coated with or containing the active compound. The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.

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

In addition, the active compound may also be used for the treatment of seeds from plants, which have been modified by mutagenisis or genetic engineering, and which e.g. tolerate the action of herbicides or fungicides or insecticides. Conventional seed treatment formulations include e.g. flowable concentrates FS, solutions LS, suspoemulsions (SE), powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. Preferably, the formulations are applied such that germination is not included.

The active substance concentrations in ready-to-use formulations, which may be obtained after two-to-tenfold dilution, are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40% by weight.

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

Especially preferred FS formulations of the compounds of the invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20% by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5% by weight of a wetter and from 0.5 to 15% by weight of a dispersing agent, up to 20% by weight, e.g. from 5 to 20% of an anti-freeze agent, from 0 to 15% by weight, e.g. 1 to 15% by weight of a pigment and/or a dye, from 0 to 40% by weight, e.g. 1 to 40% by weight of a binder (sticker/adhesion agent), optionally up to 5% by weight, e.g. from 0.1 to 5% by weight of a thickener, optionally from 0.1 to 2% of an anti-foam agent, and optionally a preservative e.g. a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1% by weight and a filler/vehicle up to 100% by weight.

In the treatment of seed, the application rates of the compounds of the invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.

The invention therefore also relates to seed comprising a compound of the invention, or an agriculturally useful salt thereof, as defined herein. The amount of the compound of the invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops e.g. lettuce the rate can be higher.

Biological Examples of the Invention

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

Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds (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 yBLISS is the expected effect based on the single effects of compound y1 and y2, respectively (1). yBuss = yi +y2 — yiy? 1

An R-script called "syngergyfinder” based on the model above was published by He, L. et al. (2018).

The latest up-date was published by:

Zheng S, Wang W, Aldahdooh J, Malyutina A, Shadbahr T, Tanoli Z, Pessia A, Tang J (2022). "SynergyFinder Plus: Toward Better Interpretation and Annotation of Drug Combination Screening Datasets.” Genomics, Proteomics & Bioinformatics, 20 (3): 587-596. https://doi.Org/10.1016/j.gpb.2022.01.004.

It can be also downloaded from Bioconductor.org: https://bioconductor.ora/packaaes/release/bioc/html/syneravfinder.html

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

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 analysis of synergism or antagonism between the mixtures or compositions can be determined using Colby's equation. If not otherwise specified, the test solutions are prepared as follow:

The active compound is dissolved at the desired concentration in a mixture of 1 :1 (vokvol) distilled water : acteone. The test solution is prepared at the day of use.

Test solutions are prepared in general at concentrations of 1000 ppm, 500 ppm, 300 ppm, 100 ppm and 30 ppm (wt/vol).

Test 1 : Yellow fever mosquito (Aedes aegypti)

For evaluating control of yellow fever mosquito {Aedes aegypti) the test unit consisted of 96-wel l-microtiter plates containing 200pil 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 2.5pil, 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

Test 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 5pil, 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 2

*synergistic control effect according to Colby's equation Test 3: Tobacco budworm Heliothis virescens)

For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96-wel l-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 10pil, using a custom-built mi- cro 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 5 days. Both, egg and larval mortality was then visually assessed and given a score (0, 50, or 100% control effect).

Table 3

*synergistic control effect according to Colby's equation

Test 4: 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. 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, 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 4

*synergistic control effect according to Colby's equation

Test 5: Diamondback Moth (Plutella xylostella)

For evaluating control of Diamondback Moth {Plutella xylostella) the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 P. xylostella 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 10pil, using a custom-built micro atomizer.

For experimental mixtures in these tests, identical volumes of both mixing partners at the desired concentrations re- spectively, 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 5 days. Both, egg and larval mortality was then visually assessed and given a score (0, 50, or 100% control effect).

Table 5

*synergistic control effect according to Colby's equation

Further, the following tests can be used to determine the pesticidal activity and a potential synergistic activity: Fungicidal microtests

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

The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. In the present tests, the compound of formula I was employed as a racemate (compound l-rac).

The test was performed as described for each pathogen below.

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. 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.

Test F1. Activity against the grey mold Botrytis cinerea in the microtiterplate test (BOTRCI)

A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added.

Table F1

Test F2. Activity against rice blast Pyricularia oryzae in the microtiterplate test (PYRIOR)

A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.

Table F2 Test F3. Activity against leaf blotch on wheat caused by Septoria tritici (SEPTTR)

A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added. Table F3

Test F4. Activity against anthracnose caused by Colletotrichum orbiculare in the microtiterplate test (COLLLA) A spore suspension of Colletotrichum orbiculare in an aqueous bio malt solution was then added.

Table F4

Claims

Claims:

1. Pesticidal mixtures comprising as active components

A) the compound A which is the compound of formula I : and

B) at least one further compound B selected from Insecticides from groups 1 to 11 :

1) M.2 GABA-gated chloride channel antagonists: fipronil;

2) M.3 pyrethroids: lambda-cyhalothrin, bifenthrin, tefluthrin, alpha-cypermethrin;

3) M.4 nAChR agonists: thiamethoxam, clothianidin, acetamiprid, imidacloprid, dinotefuran, sulfoxaflor, tri- flumezopyrim;

4) M.5: spinosyns: spinosad and spinetoram;

5) M.6 avermectins: abamectin;

7) M.22 Voltage-dependent sodium channel blocker: indoxacarb; metaflumizone;

8) M.23 Inhibitors of the of acetyl CoA carboxylase: spiropidion, spidoxamat;

9) M.28 Ryanodine receptor-modulators: chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole;

10) M.30: broflanilide;

11) M.UN: dimpropyridaz, afidopyropen, 1-[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5- ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile) , 6-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro- 7-methy l-[1 , 3] d ioxolo [4, 5-f] benzi mid azole) ; and fungicides from groups 12 to 15:

12) inhibitors of ergosterol-biosynthesis: difenoconazole, prothioconazole, flutriafol, ipconazole, tebucona- zole, mefentrifluconazole, triticonazole, fluoxytioconazol;

13) strobilurins: metyltetraprole, azoxystrobin, trifloxystrobin, pyraclostrobin;

14) SDHIs: sedaxane, penflufen, fluopyram, fluxapyroxad, pydiflumetofen, isoflucypram, cyclobutrifluram;

15) further classes: oxathiapiprolin, fluoxapriprolin, metalaxyl, picarbutrazox, fludioxonil, thiabendazole, thiram, thiophanat-methyl; wherein component A and component B are present in a weight ratio of from 1000:1 to 1 :1000.

2. The mixtures of claim 1 wherein component B) is selected from fipronil, lambda-cyhalothrin, bifenthrin, tefluthrin, alpha-cypermethrin, thiamethoxam, clothianidin, acetamiprid, imidacloprid, spinosad, spinetoram, abamectin, indoxacarb; spiropidion, spidoxamat, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, broflanilide and dimpropyridaz.

3. The mixtures of claim 1 wherein component B) is selected from lambda-cy halothrin, bifenthrin, tefluthrin, al- pha-cypermethrin, clothianidin, spinosad, abamectin, chlorantraniliprole and broflanilide.

4. The mixtures of claim 1 wherein component B) is selected from prothioconazole, tebuconazole, cyclobutriflu- ram, oxathiapiprolin, fludioxonil.

5. The mixtures of claim 1 wherein component B) is selected from M.3 pyrethroids I ambda-cy halothri n, bifenthrin, tefluthrin and alpha-cypermethrin.

6. The mixtures of claim 1 wherein component B) is selected from M.4 nAChR agonists thiamethoxam, clothianidin, acetamiprid, and imidacloprid; or selected from thiamethoxam, clothianidin and acetamiprid, or clothianidin.

7. The mixtures of claim 1 wherein component B) is selected from spinosad and spinetoram, or is spinosad.

8. The mixtures of claim 1 wherein component B) is abamectin.

9. The mixtures of claim 1 wherein component B) is selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole and tetraniliprole; or selected from chlorantraniliprole and cyantraniliprole, or selected from chlorantraniliprole.

10. The mixtures of claim 1 wherein component B) is broflanilide.

11. A composition comprising a pesticidal mixture according to any one of claims 1 to 10 and at least one inert liquid and/or solid carrier.

12. An agricultural composition for combating animal pests comprising a pesticidal mixture according to any one of claims 1 to 10 and at least one inert liquid and/or solid acceptable carrier and optionally at least one surfactant.

13. A method for combating or controlling invertebrate pests or harmful pathogenic fungi, 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 10.

14. A method for protecting growing plants or plant propagation materials from attack or infestation by invertebrate pests or harmful pathogenic fungi, 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 10.

15. A method for protection of plant propagation material comprising contacting the plant propagation material with the pesticidal mixture as defined in any of claims 1 to 10 in an amount of from 0.1 g to 10 kg per 100 kg of plant propagation material.