EP3927165A1 - Pesticidal mixtures - Google Patents

Pesticidal mixtures

Info

Publication number
EP3927165A1
EP3927165A1 EP20703761.5A EP20703761A EP3927165A1 EP 3927165 A1 EP3927165 A1 EP 3927165A1 EP 20703761 A EP20703761 A EP 20703761A EP 3927165 A1 EP3927165 A1 EP 3927165A1
Authority
EP
European Patent Office
Prior art keywords
group
compound
mixture
plant
heteroaryl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20703761.5A
Other languages
German (de)
French (fr)
Inventor
Markus Gewehr
Jurith Montag
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3927165A1 publication Critical patent/EP3927165A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms

Definitions

  • the present invention relates to fungicidal mixtures comprising
  • Ri is selected from
  • R2 is selected from the group consisting of CH3, C2H5, 1-C3H7;
  • R3 1S selected from the group consisting of H, Ci-C6-alkyl
  • R3 1S selected from the group consisting of H, Ci-C6-alkyl
  • R3 and R3 ⁇ together with the carbon atom to which they are bound form C3-C6-cycloalkyl, 5- and 6-membered aryl or heteroaryl, wherein the heteroaryl may further contain 1 , 2, 3 or 4 heteroa toms selected from N-RN, O and S, wherein RN IS selected from H, Ci-C4-alkyl; and
  • aryl or heteroaryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maxi mum number of identical or different groups R3, 3 ⁇ which independently of one another are se lected from:
  • R4 is selected from the group consisting of 5- and 6-membered aryl or heteroaryl, wherein the heteroaryl may further contain 1 , 2, 3 or 4 heteroatoms selected from N-RN, O and
  • RN IS selected from H, Ci-C4-alkyl
  • aryl or heteroaryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maxi mum number of identical or different groups R4A which independently of one another are select ed from:
  • R4A halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogen cycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio;
  • the invention relates to a method for controlling pests, this includes animal pests and harmful fungi, using the inventive mixtures and the use of compound I and compound II for pre paring such mixtures, and also compositions comprising such mixtures.
  • the present invention also comprises a method for protection of plant propagation material (preferably seed) from harmful fungi or comprising contacting the plant propagation materials (preferably seeds) with an inventive mixture in pesticidally effective amounts
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. pota toes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
  • propagation material denotes seeds.
  • the present invention also comprises a method for protection of plant propagation material (preferably seed) from harmful fungi comprising contacting the plant propagation mate rials (preferably seeds) with the inventive mixture in pesticidally effective amounts.
  • the invention relates to a method for controlling harmful fungi using the inventive mix tures and to the use of the compounds present in the inventive mixtures for preparing such mix tures, and also to compositions comprising such mixtures.
  • the present invention further relates to plant-protecting active ingredient mixtures having syner- gisti cally enhanced activity of improving the health of plants and to a method of applying such inventive mixtures to the plants.
  • Compound I and analogues as well as its pesticidal activity and methods for producing it are known e.g. from WO 2013/162072.
  • Compound II as well as its pesticidal activity and methods for producing it are known from known from WO2018129238.
  • pests embrace harmful fungi and animal pests.
  • Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of harmful fungi and harmful animal pests.
  • plant health Another problem underlying the present invention is the desire for compositions that improve plants, a process which is commonly and hereinafter referred to as“plant health”.
  • plant health comprises various sorts of improvements of plants that are not connected to the control of pests.
  • advantageous properties are im proved crop characteristics including: emergence, crop yields, protein content, oil content, starch content, more developed root system (improved root growth), improved stress tolerance (e.g.
  • tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, enhanced plant vigor, increased plant stand and early and better germination; or any other advantages familiar to a person skilled in the art.
  • Ri is selected from
  • R2 is selected from the group consisting of CH3, C2H5, 1-C3H7;
  • R3 1S selected from the group consisting of H, Ci-C6-alkyl
  • R3 1S selected from the group consisting of H, Ci-C6-alkyl
  • R3 and R3 ⁇ together with the carbon atom to which they are bound form C3-C6-cycloalkyl, 5- and 6-membered aryl or heteroaryl, wherein the heteroaryl may further contain 1 , 2, 3 or 4 heteroa toms selected from N-RN, O and S, wherein RN is selected from H, Ci-C4-alkyl; and
  • aryl or heteroaryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maxi mum number of identical or different groups R3, 3 ⁇ which independently of one another are se lected from:
  • R4 is selected from the group consisting of 5- and 6-membered aryl or heteroaryl, wherein the heteroaryl may further contain 1 , 2, 3 or 4 heteroatoms selected from N-RN, O and
  • RN IS selected from H, Ci-C4-alkyl
  • aryl or heteroaryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maxi mum number of identical or different groups R4A which independently of one another are select ed from:
  • R4A halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogen cycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio;
  • W is S or O.
  • the mixtures as defined in the outset show markedly en hanced activity against pests compared to the control rates that are possible with the individual compounds and/or is suitable for improving the health of plants when applied to plants, parts of plants, seeds, or at their locus of growth.
  • the ratio by weight of compound I and compound II in binary mixtures is from 10000:1 to 1 :10000, from 500:1 to 1 :500, preferably from 100:1 to 1 :100 more preferably from 50:1 to 1 :50, most preferably from 20:1 to 1 :20, including also ratios from 10:1 to 1 :10, 1 :5 to 5:1 , or 1 :1.
  • compound II present in the inventive mix tures is a compound of formula II with Ri is selected from
  • R3 1S selected from the group consisting of H, Ci-C6-alkyl
  • R3 is selected from the group consisting of H, Ci-C6-alkyl
  • R3 and R3 ⁇ together with the carbon atom to which they are bound form C3-C6-cycloalkyl
  • R4 1S selected from the group consisting of 6-membered aryl
  • aryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maximum number of identical or different groups R4A which independently of one another are selected from:
  • R4A halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogen cycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio;
  • W is S or O.
  • compound II present in the inventive mixtures is a compound of formula II with Ri is selected from
  • R3 1S selected from the group consisting of H, CH3, C2H5;
  • R3 is selected from the group consisting of H, CH3, C2H5;
  • R3 and R3 ⁇ together with the carbon atom to which they are bound form C3-C6-cycloalkyl
  • R4 1S selected from the group consisting of 6-membered aryl
  • aryl is unsubstituted or substituted in the position 2 and 4 with identical or different groups R4A which independently of one another are selected from:
  • W is S or O.
  • compound II present in the inventive mixtures is a compound of formula II with
  • R2 1S Methyl, R33 1S Methyl, R4 is selected from the group consisting of 5- and 6-membered aryl or heteroaryl, wherein the
  • W is oxygen
  • compound II present in the inventive mixtures is selected from the group consisting of [(1S,2S)-2-(4-fluoro-2-methyl- phenyl)-1 , 3-dimethyl-butyl] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2- carbonyl)amino]propanoate, [(1S,2S)-2-(2,4-dimethylphenyl)-1 ,3-dimethyl-butyl] (2S)-2-[(3- hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate, [(1S,2S)-2-(2,4-difluorophenyl)-1 ,3- dimethyl-butyl] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate, [(1S,2S)-2- (2-fluoro-4-methyl-phen
  • compound II has the following formula:
  • compound II has the following formula: In one embodiment, compound II has the following formula:
  • compound II has the following formula:
  • compound II has the following formula:
  • compound II has the following formula:
  • compound II has the following formula: In one embodiment, compound II has the following formula:
  • compound II has the following formula:
  • compound II has the following formula:
  • compound II has the following formula:
  • the inventive mixtures can further contain one or more insecticides, fungicides, herbicides.
  • 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.
  • compositions types are defined in the“Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New develop ments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, disper sants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibil- izers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • the resulting agrochemical compositions generally comprise between 0.01 and 95%, pref erably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active sub stance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), pow ders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually em ployed for the purposes of treatment of plant propagation materials, particularly seeds.
  • the compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Appli cation can be carried out before or during sowing.
  • inventive mixtures and compositions thereof are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances applied are, depend ing on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.01 to 1.0 kg per ha, and in particular from 0.05 to 0.75 kg per ha.
  • active substance In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.01-10 kg, preferably from 0.1-1000 g, more preferably from 1-100 g per 100 kilogram of plant propagation material (preferably seeds) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides may be added to the ac- tive substances or the compositions comprising them as premix or, if appropriate not until im mediately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions accord ing to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • the user applies the composition according to the invention usually from a predosage de vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the ag rochemical 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.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • individual components of the composition according to the in vention such as parts of a kit or parts of a binary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pel leting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pel leting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • one embodiment of the invention is a kit for preparing a usable pesticidal com position, the kit comprising a) a composition comprising component 1) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and option ally a further active component 3) as defined herein.
  • the present invention comprises a method for controlling harmful fungi, wherein the pest, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or plant propagation material (preferably seed) are treated with a pesticidally effective amount of an inventive mixture.
  • the mixtures according to the present invention are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
  • fungi are particularly important for controlling a multitude of fungi on various cultivated plants, such as bananas, cotton, vegetable species (for example cucumbers, beans and cucurbits), cereals such as wheat, rye, barley, rice, oats; grass coffee, potatoes, corn, fruit species, soya, tomatoes, grapevines, ornamental plants, sugar cane and also on a large number of seeds.
  • the inventive mixtures are used in soya (soybean), cereals and corn.
  • the inventive mixtures are suitable for controlling the following fungal diseases on soybeans: Alternaria spp. (Alternaria leaf spot); Cercospora spp. (Cercospora leaf spots), e. g. C. sojina or C. kikuchii); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose), e. g. C. truncatum or C. gloeosporioides); Corynespora cassiicola (leaf spots); Diaporthe spp., e. g. D. phaseolorum (damping off); Fusarium (teleomorph: Gibberella) spp.
  • the mixtures according to the present invention are particularly important for controlling phyto pathogenic harmful fungi on soybean.
  • the mixtures according to the present invention are also particularly important for controlling Phakopsora pachyrhizi and P. meibomiae (soybean rust).
  • the mixtures according to the present invention are also particularly important for controlling Cercospora sojina, Cercospora kikuchii or Corynospera cassiicula on soybean
  • Mixtures according to the invention are suitable for combating phytopathogenic fungi, such fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibi tors, wherein the mutation is G143A or F129L.
  • the term“cereals” comprises wheat or barley.
  • Resistant fungi on wheat or barley in the course of the use of the present invention, wherein the mutation is G143A are Septoria tritici, (leaf blotch) on wheat, Microduchium nivale, (head blight) on wheat, Blumeria graminis f. sp. tritici, (powdery mildew) on wheat, Phaesphaeria nodorum, (leaf blotch) on wheat, Pyrenophora tritici-repentis, (tan spot) on wheat, Rhynchosporium secal- is, (leaf blotch) on barley, Blumeria graminis f. sp. hordei, (powdery mildew) on barley and Ramularia collo-cygni, (leaf spot) on barley.
  • the resistant fungi on wheat or barley in the course of the use of the present invention, wherein the mutation is F129L is Pyrenophora teres, (net blotch) on barley.
  • Cercospora sojina (frogeye leaf spot) and Corynespora cassiicola (target spot).
  • pesticidally effective amount means the amount of the inventive mixtures or of compositions comprising the mixtures needed to achieve an observable effect on growth, in cluding the effects of necrosis, death, retardation, prevention, and removal, destruction, or oth erwise 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 mixtures / compositions will also vary according to the prevailing condi tions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the present invention comprises a method for improving the health of plants, wherein the plant, the locus where the plant is growing or is expected to grow or plant propaga tion material, from which the plant grows, is treated with a plant health effective amount of an inventive mixture.
  • plant effective amount denotes an amount of the inventive mixtures, which is suffi cient for achieving plant health effects as defined herein below. More exemplary information about amounts, ways of application and suitable ratios to be used is given below. Again, the skilled artisan is well aware of the fact that such an amount can vary in a broad range and is dependent on various factors, e.g. the treated cultivated plant or material and the climatic condi tions.
  • inventive mixtures are employed by treating the fungi or the plants, plant propagation materials (preferably seeds), materials or soil to be protected from fungal attack with a pesticidally effective amount of the active compounds.
  • the application can be carried out both before and after the infection of the materials, plants or plant propagation materials (preferably seeds) by the pests.
  • the term plant refers to an entire plant, a part of the plant or the propagation material of the plant.
  • inventive mixtures and compositions thereof are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • cereals e. g. wheat, rye, barley, triticale, oats or rice
  • beet e. g. sugar beet or fodder beet
  • fruits such as pomes, stone fruits or soft fruits, e. g.
  • the inventive mixtures and compositions thereof are used for con trolling a multitude of fungi on field crops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • field crops such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • treatment of plant propagation materials with the inventive mixtures and compo sitions thereof, respectively is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; potatoes, tomatoes, vines, rice, corn, cotton and soybeans.
  • cultiva plants is to be understood as including plants which have been modi fied by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-qmc.org/, see GM crop data- base therein).
  • Genetically modified plants are plants, which genetic material has been so modi fied by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not lim ited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by gly- cosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • Plants include that have been modified by breeding, mutagenesis or genetic engineering.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins,.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens..
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass produc tion, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • productivity e. g. bio mass produc tion, grain yield, starch content, oil content or protein content
  • plants are also covered that contain by the use of recombinant DNA tech niques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition.
  • plants are also covered that contain by the use of recombinant DNA tech niques a modified amount of substances of content or new substances of content, specifically to improve raw material production.
  • the separate or joint application of the compounds of the inventive mixtures is carried out by spraying or dusting the seeds, the seedlings, the plants or the soils before or after sowing of the plants or before or after emergence of the plants.
  • Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .
  • the content of the mixture of the active ingredients is from 0.001 to 80 weight %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
  • the active compounds were formulated separately as a stock solution having a concen- tration 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.
  • MTP micro titer plate
  • a spore suspension of Pyricularia oryzae 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 ab sorption photometer, the MTPs were measured at 405 n 7 days after the inoculation.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Microdochium nivale 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 ab sorption 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.
  • An efficacy of 0 means that the growth level of the pathogens corresponds to that of the un treated control; an efficacy of 100 means that the pathogens were not growing.

Abstract

Fungicidal mixtures comprising, as active components, 1) 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol- 5-one as compound I and 2) one fungicidal compound II of formula II

Description

Pesticidal mixtures
The present invention relates to fungicidal mixtures comprising
1 ) 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one as compound I and
2) one fungicidal compound II of formula II
wherein
Ri is selected from
R2 is selected from the group consisting of CH3, C2H5, 1-C3H7; and
R3 1S selected from the group consisting of H, Ci-C6-alkyl;
R3 1S selected from the group consisting of H, Ci-C6-alkyl;
R3 and R3· together with the carbon atom to which they are bound form C3-C6-cycloalkyl, 5- and 6-membered aryl or heteroaryl, wherein the heteroaryl may further contain 1 , 2, 3 or 4 heteroa toms selected from N-RN, O and S, wherein RN IS selected from H, Ci-C4-alkyl; and
wherein S may be in the form of its oxide SO or SO2; and wherein in each case one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently selected from C(=0) and C(=S); and
wherein the aryl or heteroaryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maxi mum number of identical or different groups R3, 3· which independently of one another are se lected from:
R3, 3· halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio;
R4 is selected from the group consisting of 5- and 6-membered aryl or heteroaryl, wherein the heteroaryl may further contain 1 , 2, 3 or 4 heteroatoms selected from N-RN, O and
S, wherein RN IS selected from H, Ci-C4-alkyl; and
wherein S may be in the form of its oxide SO or SO2; and wherein in each case one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently selected from C(=0) and C(=S); and
wherein the aryl or heteroaryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maxi mum number of identical or different groups R4A which independently of one another are select ed from:
R4A halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogen cycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio;
R5 1S selected from the group consisting of H, -C(=0)CH3, -CH20C(C0)CH(CH3)2; and W is S or O.
Moreover, the invention relates to a method for controlling pests, this includes animal pests and harmful fungi, using the inventive mixtures and the use of compound I and compound II for pre paring such mixtures, and also compositions comprising such mixtures.
Additionally, the present invention also comprises a method for protection of plant propagation material (preferably seed) from harmful fungi or comprising contacting the plant propagation materials (preferably seeds) with an inventive mixture in pesticidally effective amounts
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. pota toes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring. In a particular preferred embodiment, the term propagation material denotes seeds.
Additionally, the present invention also comprises a method for protection of plant propagation material (preferably seed) from harmful fungi comprising contacting the plant propagation mate rials (preferably seeds) with the inventive mixture in pesticidally effective amounts.
Moreover, the invention relates to a method for controlling harmful fungi using the inventive mix tures and to the use of the compounds present in the inventive mixtures for preparing such mix tures, and also to compositions comprising such mixtures.
The present invention further relates to plant-protecting active ingredient mixtures having syner- gisti cally enhanced activity of improving the health of plants and to a method of applying such inventive mixtures to the plants.
Compound I and analogues as well as its pesticidal activity and methods for producing it are known e.g. from WO 2013/162072. Compound II as well as its pesticidal activity and methods for producing it are known from known from WO2018129238.
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 toxicolog ical effects whilst still allowing effective pest control.
In regard to the instant invention the term pests embrace harmful fungi and animal pests.
Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of harmful fungi and harmful animal pests.
There also exists the need for pest control agents that combine knock-down activity with pro longed control, that is, fast action with long lasting action. Another difficulty in relation to the use of pesticides is that the repeated and exclusive applica tion of an individual pesticidal compound leads in many cases to a rapid selection of pests, that means animal pests, and harmful fungi, which have developed natural or adapted resistance against the active compound in question. Therefore, there is a need for pest control agents that help prevent or overcome resistance.
Another problem underlying the present invention is the desire for compositions that improve plants, a process which is commonly and hereinafter referred to as“plant health”.
The term plant health comprises various sorts of improvements of plants that are not connected to the control of pests. For example, advantageous properties that may be mentioned are im proved crop characteristics including: emergence, crop yields, protein content, oil content, starch content, more developed root system (improved root growth), improved stress tolerance (e.g. against drought, heat, salt, UV, water, cold), reduced ethylene (reduced production and/or inhibition of reception), tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, enhanced plant vigor, increased plant stand and early and better germination; or any other advantages familiar to a person skilled in the art.
It was therefore an object of the present invention to provide pesticidal mixtures which solve the problems of reducing the dosage rate and / or enhancing the spectrum of activity and / or com bining knock-down activity with prolonged control and / or to resistance management and/or promoting the health of plants.
We have found that this object is in part or in whole achieved by the fungicidal mixtures com prising
1 ) 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one as compound I and
2) one fungicidal compound II of formula II
wherein
Ri is selected from
R2 is selected from the group consisting of CH3, C2H5, 1-C3H7; and
R3 1S selected from the group consisting of H, Ci-C6-alkyl;
R3 1S selected from the group consisting of H, Ci-C6-alkyl;
R3 and R3· together with the carbon atom to which they are bound form C3-C6-cycloalkyl, 5- and 6-membered aryl or heteroaryl, wherein the heteroaryl may further contain 1 , 2, 3 or 4 heteroa toms selected from N-RN, O and S, wherein RN is selected from H, Ci-C4-alkyl; and
wherein S may be in the form of its oxide SO or SO2; and wherein in each case one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently selected from C(=0) and C(=S); and
wherein the aryl or heteroaryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maxi mum number of identical or different groups R3, 3· which independently of one another are se lected from:
R3, 3· halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio;
R4 is selected from the group consisting of 5- and 6-membered aryl or heteroaryl, wherein the heteroaryl may further contain 1 , 2, 3 or 4 heteroatoms selected from N-RN, O and
S, wherein RN IS selected from H, Ci-C4-alkyl; and
wherein S may be in the form of its oxide SO or SO2; and wherein in each case one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently selected from C(=0) and C(=S); and
wherein the aryl or heteroaryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maxi mum number of identical or different groups R4A which independently of one another are select ed from:
R4A halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogen cycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio;
R5 1S selected from the group consisting of H, -C(=0)CH3, -CH20C(C0)CH(CH3)2; and
W is S or O.
Especially, it has been found that the mixtures as defined in the outset show markedly en hanced activity against pests compared to the control rates that are possible with the individual compounds and/or is suitable for improving the health of plants when applied to plants, parts of plants, seeds, or at their locus of growth.
It has been found that the activity of the inventive mixtures comprising compound I and com pound II goes far beyond the fungicidal and/or plant health improving activity of the active com pounds present in the mixture alone (synergistic activity).
Moreover, we have found that simultaneous, that is joint or separate, application of the com pound I and the compound II or successive application of the compound I and the compound II allows enhanced control of harmful fungi, compared to the control rates that are possible with the individual compounds (synergistic mixtures).
Moreover, we have found that simultaneous, that is joint or separate, application of the com pound I and the compound II or successive application of the compound I and the compound II provides enhanced plant health effects compared to the plant health effects that are possible with the individual compounds. The ratio by weight of compound I and compound II in binary mixtures is from 10000:1 to 1 :10000, from 500:1 to 1 :500, preferably from 100:1 to 1 :100 more preferably from 50:1 to 1 :50, most preferably from 20:1 to 1 :20, including also ratios from 10:1 to 1 :10, 1 :5 to 5:1 , or 1 :1.
In a preferred embodiment of the inventive mixtures, compound II present in the inventive mix tures is a compound of formula II with Ri is selected from
R2 1S CH3; and
R3 1S selected from the group consisting of H, Ci-C6-alkyl;
R3 is selected from the group consisting of H, Ci-C6-alkyl;
R3 and R3· together with the carbon atom to which they are bound form C3-C6-cycloalkyl;
R4 1S selected from the group consisting of 6-membered aryl,
wherein the aryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maximum number of identical or different groups R4A which independently of one another are selected from:
R4A halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogen cycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio;
R5 1S selected from the group consisting of H, -C(=0)CH3, -CH20C(C0)CH(CH3)2; and
W is S or O.
In another preferred embodiment of the inventive mixtures, compound II present in the inventive mixtures is a compound of formula II with Ri is selected from
R2 1S CH3; and
R3 1S selected from the group consisting of H, CH3, C2H5;
R3 is selected from the group consisting of H, CH3, C2H5;
R3 and R3· together with the carbon atom to which they are bound form C3-C6-cycloalkyl;
R4 1S selected from the group consisting of 6-membered aryl,
wherein the aryl is unsubstituted or substituted in the position 2 and 4 with identical or different groups R4A which independently of one another are selected from:
R4ACH3, F;
R5 1S selected from the group consisting of H, -C(=0)CH3, -CH20C(C0)CH(CH3)2; and
W is S or O. In a particularly preferred embodiment of the inventive mixtures, compound II present in the inventive mixtures is a compound of formula II with
Ri is
R2 1S Methyl, R33 1S Methyl, R4 is selected from the group consisting of 5- and 6-membered aryl or heteroaryl, wherein the
R5 1S selected from the group consisting of H, -C(=0)CH3, -CH20C(C0)CH(CH3)2; and
W is oxygen.
In a further particularly preferred embodiment of the inventive mixtures, compound II present in the inventive mixtures is selected from the group consisting of [(1S,2S)-2-(4-fluoro-2-methyl- phenyl)-1 , 3-dimethyl-butyl] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2- carbonyl)amino]propanoate, [(1S,2S)-2-(2,4-dimethylphenyl)-1 ,3-dimethyl-butyl] (2S)-2-[(3- hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate, [(1S,2S)-2-(2,4-difluorophenyl)-1 ,3- dimethyl-butyl] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate, [(1S,2S)-2- (2-fluoro-4-methyl-phenyl)-1 , 3-dimethyl-butyl] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2- carbonyl)amino]propanoate, [(1S,2S)-2-(4-fluoro-2-methyl-phenyl)-1 , 3-dimethyl-butyl] (2S)-2-[(3- acetoxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate, [(1 S,2S)-2-(2,4-dimethylphenyl)-1 ,3- dimethyl-butyl] (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate, [(1S,2S)-2- (2, 4-difluorophenyl)-1 , 3-dimethyl-butyl] (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2- carbonyl)amino]propanoate, [(1S,2S)-2-(2-fluoro-4-methyl-phenyl)-1 , 3-dimethyl-butyl] (2S)-2-[(3- acetoxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate, [2-[[(1 S)-2-[(1 S,2S)-2-(4-fluoro-2- methyl-phenyl)-1 ,3-dimethyl-butoxy]-1-methyl-2-oxo-ethyl]carbamoyl]-4-methoxy-3- pyridyl]oxymethyl 2-methylpropanoate, [2-[[(1S)-2-[(1S,2S)-2-(2,4-dimethylphenyl)-1 ,3-dimethyl- butoxy]-1-methyl-2-oxo-ethyl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate, [2-[[(1S)-2-[(1S,2S)-2-(2,4-difluorophenyl)-1 ,3-dimethyl-butoxy]-1-methyl-2-oxo- ethyl]carbamoyl]-4-methoxy-3-pyridyl]oxymethyl 2-methylpropanoate and [2-[[(1S)-2-[(1S,2S)-2- (2-fluoro-4-methyl-phenyl)-1 ,3-dimethyl-butoxy]-1-methyl-2-oxo-ethyl]carbamoyl]-4-methoxy-3- pyridyl]oxymethyl 2-methylpropanoate.
In one embodiment, compound II has the following formula:
In one embodiment, compound II has the following formula: In one embodiment, compound II has the following formula:
In one embodiment, compound II has the following formula:
In one embodiment, compound II has the following formula:
In one embodiment, compound II has the following formula:
In one embodiment, compound II has the following formula: In one embodiment, compound II has the following formula:
In one embodiment, compound II has the following formula:
In one embodiment, compound II has the following formula:
In one embodiment, compound II has the following formula:
All above-referred mixtures are herein below referred to as“inventive mixtures” or“mixtures according to the invention”.
The inventive mixtures can further contain one or more insecticides, fungicides, herbicides.
The inventive mixtures can be converted into customary types of agrochemical composi tions, 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 such as 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, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New develop ments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, disper sants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibil- izers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
The resulting agrochemical compositions generally comprise between 0.01 and 95%, pref erably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active sub stance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), pow ders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually em ployed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Appli cation can be carried out before or during sowing. Methods for applying the inventive mixtures and compositions thereof, respectively, on to plant propagation material, especially seeds in clude dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, the inventive mixtures or the compositions thereof, respective ly, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
When employed in plant protection, the amounts of active substances applied are, depend ing on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.01 to 1.0 kg per ha, and in particular from 0.05 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.01-10 kg, preferably from 0.1-1000 g, more preferably from 1-100 g per 100 kilogram of plant propagation material (preferably seeds) are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the ac- tive substances or the compositions comprising them as premix or, if appropriate not until im mediately prior to use (tank mix). These agents can be admixed with the compositions accord ing to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
The user applies the composition according to the invention usually from a predosage de vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the ag rochemical 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, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, individual components of the composition according to the in vention such as parts of a kit or parts of a binary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pel leting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal com position, the kit comprising a) a composition comprising component 1) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and option ally a further active component 3) as defined herein.
As said above, the present invention comprises a method for controlling harmful fungi, wherein the pest, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or plant propagation material (preferably seed) are treated with a pesticidally effective amount of an inventive mixture.
The mixtures according to the present invention are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
They are particularly important for controlling a multitude of fungi on various cultivated plants, such as bananas, cotton, vegetable species (for example cucumbers, beans and cucurbits), cereals such as wheat, rye, barley, rice, oats; grass coffee, potatoes, corn, fruit species, soya, tomatoes, grapevines, ornamental plants, sugar cane and also on a large number of seeds. In a preferred embodiment, the inventive mixtures are used in soya (soybean), cereals and corn.
More preferably, the inventive mixtures are suitable for controlling the following fungal diseases on soybeans: Alternaria spp. (Alternaria leaf spot); Cercospora spp. (Cercospora leaf spots), e. g. C. sojina or C. kikuchii); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose), e. g. C. truncatum or C. gloeosporioides); Corynespora cassiicola (leaf spots); Diaporthe spp., e. g. D. phaseolorum (damping off); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot), e.g. F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans; Mac- rophomina phaseolina (syn. phaseoli) (root and stem rot); Peronospora spp. (downy mildew), e. g. P. manshurica ; Phakopsora pachyrhizi and P. meibomiae (soybean rust); Phomopsis spp., e. g. stem rot: P. phaseoli (teleomorph: Diaporthe phaseolorum); Phytophthora spp. (wilt, root, leaf, fruit and stem root), e. g. P. megasperma, syn. P. sojae); Rhizoctonia spp., e. g. R. solani (root and stem rot); Septoria spp., e. g. S. glycines (brown spot). The mixtures according to the present invention are particularly important for controlling phyto pathogenic harmful fungi on soybean.
The mixtures according to the present invention are also particularly important for controlling Phakopsora pachyrhizi and P. meibomiae (soybean rust).
The mixtures according to the present invention are also particularly important for controlling Cercospora sojina, Cercospora kikuchii or Corynospera cassiicula on soybean
Mixtures according to the invention are suitable for combating phytopathogenic fungi, such fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibi tors, wherein the mutation is G143A or F129L.
The term“cereals” comprises wheat or barley.
These Fungi on wheat or barley containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, wherein the mutation is G143A or F129L, are hereinafter referred to as“resistant fungi”.
Resistant fungi on wheat or barley in the course of the use of the present invention, wherein the mutation is G143A are Septoria tritici, (leaf blotch) on wheat, Microduchium nivale, (head blight) on wheat, Blumeria graminis f. sp. tritici, (powdery mildew) on wheat, Phaesphaeria nodorum, (leaf blotch) on wheat, Pyrenophora tritici-repentis, (tan spot) on wheat, Rhynchosporium secal- is, (leaf blotch) on barley, Blumeria graminis f. sp. hordei, (powdery mildew) on barley and Ramularia collo-cygni, (leaf spot) on barley.
The resistant fungi on wheat or barley in the course of the use of the present invention, wherein the mutation is F129L is Pyrenophora teres, (net blotch) on barley.
In soybean, the following pathogens show increasing resistance towards Qo inhibitors due to their G143A mutation:
Cercospora sojina (frogeye leaf spot) and Corynespora cassiicola (target spot).
In general, "pesticidally effective amount" means the amount of the inventive mixtures or of compositions comprising the mixtures needed to achieve an observable effect on growth, in cluding the effects of necrosis, death, retardation, prevention, and removal, destruction, or oth erwise 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 mixtures / compositions will also vary according to the prevailing condi tions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
As said above, the present invention comprises a method for improving the health of plants, wherein the plant, the locus where the plant is growing or is expected to grow or plant propaga tion material, from which the plant grows, is treated with a plant health effective amount of an inventive mixture. The term "plant effective amount" denotes an amount of the inventive mixtures, which is suffi cient for achieving plant health effects as defined herein below. More exemplary information about amounts, ways of application and suitable ratios to be used is given below. Anyway, the skilled artisan is well aware of the fact that such an amount can vary in a broad range and is dependent on various factors, e.g. the treated cultivated plant or material and the climatic condi tions.
When preparing the mixtures, it is preferred to employ the pure active compounds, to which further active compounds against pests, such as insecticides, herbicides, fungicides or else herbicidal or growth-regulating active compounds or fertilizers can be added as further active components according to need.
The inventive mixtures are employed by treating the fungi or the plants, plant propagation materials (preferably seeds), materials or soil to be protected from fungal attack with a pesticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the materials, plants or plant propagation materials (preferably seeds) by the pests.
In the context of the present invention, the term plant refers to an entire plant, a part of the plant or the propagation material of the plant.
The inventive mixtures and compositions thereof are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or mel ons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grape fruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (Table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
Preferably, the inventive mixtures and compositions thereof, respectively are used for con trolling a multitude of fungi on field crops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
Preferably, treatment of plant propagation materials with the inventive mixtures and compo sitions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; potatoes, tomatoes, vines, rice, corn, cotton and soybeans.
The term "cultivated plants" is to be understood as including plants which have been modi fied by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-qmc.org/, see GM crop data- base therein). Genetically modified plants are plants, which genetic material has been so modi fied by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not lim ited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by gly- cosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
Plants include that have been modified by breeding, mutagenesis or genetic engineering.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins,.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens..
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass produc tion, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA tech niques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition.
Furthermore, plants are also covered that contain by the use of recombinant DNA tech niques a modified amount of substances of content or new substances of content, specifically to improve raw material production.
The separate or joint application of the compounds of the inventive mixtures is carried out by spraying or dusting the seeds, the seedlings, the plants or the soils before or after sowing of the plants or before or after emergence of the plants.
Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m2 treated material, desirably from 0.1 g to 50 g per m2.
For use in spray compositions, the content of the mixture of the active ingredients is from 0.001 to 80 weight %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
The present invention offers the following advantages:
It provides pesticidal mixtures which solve the problems of reducing the dosage rate and / or excellent spectrum of activity and / or combining knock-down activity with prolonged control and / or to resistance management and/or promoting the health of plants.
Experimental Part
Microtest
The active compounds were formulated separately as a stock solution having a concen- tration of 10000 ppm in dimethyl sulfoxide.
1. 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 or DOB solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an ab sorption photometer, the MTPs were measured at 405 n 7 days after the inoculation.
2. 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 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 n 7 days after the inoculation. 3. Activity against Microdochium nivale (MONGNI)
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 Microdochium nivale 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 ab sorption 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 un treated 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.
PYRIOR
SEPTTR
MONGNI

Claims

Claims
1. Fungicidal mixtures comprising, as active components,
1 ) 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-
5-one as compound I and
2) one fungicidal compound II of formula II
wherein
Ri is selected from
R2 is selected from the group consisting of CH3, C2H5, 1-C3H7; and
R3 1S selected from the group consisting of H, Ci-C6-alkyl;
R3 1S selected from the group consisting of H, Ci-C6-alkyl;
R3 and R3· together with the carbon atom to which they are bound form C3-C6-cycloalkyl, 5- and 6-membered aryl or heteroaryl, wherein the heteroaryl may further contain 1 , 2, 3 or 4 heteroa toms selected from N-RN, O and S, wherein RN IS selected from H, Ci-C4-alkyl; and
wherein S may be in the form of its oxide SO or SO2; and wherein in each case one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently selected from C(=0) and C(=S); and
wherein the aryl or heteroaryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maxi mum number of identical or different groups R3, 3· which independently of one another are se lected from:
R3, 3· halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio;
R4 is selected from the group consisting of 5- and 6-membered aryl or heteroaryl, wherein the heteroaryl may further contain 1 , 2, 3 or 4 heteroatoms selected from N-RN, O and
S, wherein RN IS selected from H, Ci-C4-alkyl; and
wherein S may be in the form of its oxide SO or SO2; and wherein in each case one or two CH2 groups of the carbo- or heterocycle may be replaced by a group independently selected from C(=0) and C(=S); and
wherein the aryl or heteroaryl is unsubstituted or substituted with 1 , 2, 3, 4, 5 or up to the maxi mum number of identical or different groups R4A which independently of one another are select ed from:
R4A halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogen cycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio;
Rs is selected from the group consisting of H, -C(=0)CH3, -CH20C(C0)CH(CH3)2; and
W is S or O.
2. A mixture as claimed in claim 1 , wherein compound II is a compound according to formula II wherein Ri is selected from
R2 1S CH3; and
R31S selected from the group consisting of H, CH3, C2H5;
R3 1S selected from the group consisting of H, CH3, C2H5;
R3 and R3· together with the carbon atom to which they are bound form C3-C6-cycloalkyl;
R4 1S selected from the group consisting of 6-membered aryl,
wherein the aryl is unsubstituted or substituted in the position 2 and 4 with identical or different groups R4A which independently of one another are selected from:
R4ACH3, F;
R5 1S selected from the group consisting of H, -C(=0)CH3, -CH20C(C0)CH(CH3)2; and
W is S or O.
3. A mixture as claimed in any of claims 1 to 2, wherein Ri is
R2 1S Methyl, R33 1S Methyl, R4 is selected from the group consisting of 5- and 6-membered aryl or heteroaryl, wherein the
R5 1S selected from the group consisting of H, -C(=0)CH3, -CH20C(C0)CH(CH3)2;
and W is oxygen.
4. A mixture as claimed in any of claim 1 to 3, wherein the ratio by weight of compound I and compound II is from 500:1 to 1 :500.
5. A pesticidal composition, comprising a liquid or solid carrier and a mixture as defined in any of claims 1 to 4.
6. A method for controlling phytopathogenic pests, wherein the pest, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or plant prop- agation material are treated with an effective amount of a mixture or composition as de fined in any of claims 1 to 5.
7. The method according to of claim 6 for controlling phytopathogenic harmful fungi on soy bean.
8. The method according to any of claims 6 to 7 for controlling Phakopsora pachyrhizi and P. meibomiae (soybean rust).
9. The method according to any of claims 6 to 8 for controlling Cercospora sojina, C. Cerco- spora kikuchii or Corynospera cassiicula on soybean.
10. A method for improving the health of plants, wherein the plant, the locus where the plant is growing or is expected to grow or plant propagation material from which the plant grows are treated with an effective amount of a mixture or composition as defined in any of claims 1 to 5.
11. A method for protection of plant propagation material from pests comprising contacting the plant propagation materials with a mixture or composition as defined in any of claims 1 to 5 in pesticidally effective amounts.
12. A method as claimed in claim 11 , wherein the mixture as defined in any of claims 1 to 5 is applied in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation materials.
13. A method as claimed in any of claims 6 to 12, wherein the mixture as defined in any of claims 1 to 4 are applied simultaneously, that is jointly or separately, or in succession.
14. Plant propagation material, comprising the mixture as defined in any of claims 1 to 4 in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation materials.
EP20703761.5A 2019-02-21 2020-02-12 Pesticidal mixtures Withdrawn EP3927165A1 (en)

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NZ231804A (en) 1988-12-19 1993-03-26 Ciba Geigy Ag Insecticidal toxin from leiurus quinquestriatus hebraeus
ATE241699T1 (en) 1989-03-24 2003-06-15 Syngenta Participations Ag DISEASE RESISTANT TRANSGENIC PLANT
ES2074547T3 (en) 1989-11-07 1995-09-16 Pioneer Hi Bred Int LARVICID LECTINES, AND INDUCED RESISTANCE OF PLANTS TO INSECTS.
UA48104C2 (en) 1991-10-04 2002-08-15 Новартіс Аг Dna fragment including sequence that codes an insecticide protein with optimization for corn, dna fragment providing directed preferable for the stem core expression of the structural gene of the plant related to it, dna fragment providing specific for the pollen expression of related to it structural gene in the plant, recombinant dna molecule, method for obtaining a coding sequence of the insecticide protein optimized for corn, method of corn plants protection at least against one pest insect
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ES2243543T3 (en) 2000-08-25 2005-12-01 Syngenta Participations Ag HYBRIDS OF BACILLUS THURIGIENSIS CRYSTAL PROTEINS.
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BR102018000183B1 (en) 2017-01-05 2023-04-25 Dow Agrosciences Llc PICOLINAMIDES, COMPOSITION FOR CONTROLLING A FUNGAL PATHOGEN, AND METHOD FOR CONTROLLING AND PREVENTING A FUNGAL ATTACK ON A PLANT
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