PESTICIDAL MIXTURES COMPRISING A PYRAZOLE COMPOUND

Abstract

Pesticidal mixtures comprising as active compounds 1) 1-[(1RS)-1,2-dimethylpropyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-1H-pyrazole-4-carboxamide and 2) at least one further compound B selected from B.1) Succinate dehydrogenase inhibitors as defined in the specification; B.2) Inhibitors of oxysterol binding protein as defined in the specification; B.3) Inhibitors of complex III at Qi site selected from: a) florylpicoxamid, and b) fenpicox-amid; B.4) Strobilurins as defined in the specification; B.5) Inhibitors of C14-demethylase in sterol biosynthesis as defined in the specification; B.6) Inhibitors of cell division and cytoskeleton as defined in the specification, B.7) Other compounds of unknown mode of action as defined in the specification; and B.8) N-[[2-fluoro-4-[(2S,3S)-2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl]methyl]cyclopropanecarboxamide; wherein component 1) and component 2) are present in a weight ratio of from 1000:1 to 1:1000; methods and use of these mixtures for combating invertebrate pests such as insects, arachnids, nematodes and/or harmful fungi in and on plants, and for protecting such plants being infested with pests and/or harmful fungi.

Claims

1. A pesticidal mixture comprising as active components 1) 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide of formula I: ##STR00002## and 2) at least one further compound B selected from the group consisting of B.1) Succinate dehydrogenase inhibitors selected from the group consisting of a) pydiflumetofen, b) pyraziflumid, c) inpyrfluxam, d) pyrapropoyne, e) fluindapyr, f) isoflucypram, g) 2-(difluoromethyl)-N-(1,1,3-trimethyl-indan-4 yl)pyridine-3-carboxamide, h) 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylindan-4-yl]pyridine-3-carboxamide, i) 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, j) 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, k) 2-(difluoromethyl)-N-(1,1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide, 1) 2-(difluoromethyl)-N-[(3R)-1,1-dimethyl-3-propyl-indan-4-yl]-pyridine-3-carboxamide, m) 2-(difluoromethyl)-N-(3-isobutyl-1,1-dimethylindan-4-yl)¬pyridine-3-carboxamide, n) 2-(difluoromethyl)-N-[(3R)-3-isobutyl-1,1-dimethyl-indan-4 yl]pyridine-3-carboxamide, o) N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazole-4-carboxamide, and p) methyl (E)-2-[2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3-methoxy-prop-2 enoate; B.2) inhibitors of oxysterol binding protein selected from the group consisting of a) oxathiapiprolin, b) 2-{3-[2-(1-{[3,5-bis(di¬fluoro¬methyl-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2 oxazol-5-yl}¬phenyl methanesulfonate, c) 2-{3-[2-(1-{[3,5-bis(difluoro¬methyl)-1H-pyrazol-1-yl]¬acetyl}piperidin-4-yl) 1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5 yl}-3-chlorophenyl methane¬sulfonate, d) 4-[1-[2-[3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]-N-te¬tralin-1-yl-pyridine-2-carboxamide, e) 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide, f) 4-[1-[2-[3-(difluoromethyl)-5-(tri¬fluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide, g) 4-[1-[2-[5-cyclopropyl-3-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide, h) 4-[1-[2-[5-methyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-pi¬peri¬dyl]-N-tetralin-1-yl-pyridine-2-carboxamide, i) 4-[1-[2-[5-(difluoromethyl)-3-(trifluoro¬methyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide, j) 4 [1 [2-[3,5-bis(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-ylpyridine-2-carboxamide, and k) 4-[1-[2-[5-cyclopropyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-ylpyridine-2-carboxamide, B.3) Inhibitors of complex III at Qi site selected from the group consisting of: a) florylpicoxamid, and b) fenpicoxamid; B.4) Strobilurins (inhibitors of complex III, Qo site) selected from the group consisting of a) (Z,2E) 5 [1-(2,4-dichloro¬phenyl)pyrazol-3-yl]-oxy-2-methoxyimino-N,3-dimethyl-pent-3-en¬amide, b) (Z,2E) 5 [1 (4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpent-3-enamide, and c) 2-(ortho-((2,5-dimeth¬ylphenyloxy¬methylen)phenyl)-3-methoxy-acrylic acid methylester; B.5) Inhibitors of C14-demethylase in sterol biosynthesis (DMI fungicides) selected from the group consisting of a) 2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-2 pyridyl]propan-2-ol, b) 2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1 [5 [4 (trifluoromethoxy)phenyl]-2-pyridyl]propan-2-ol, c) 2-(chloromethyl)-2-methyl-5-(p-tolylmethyl)-1 (1,2,4-triazol-1 ylmethyl)cyclopentanol, and d) 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile; B.6) Inhibitors of cell division and cytoskeleton selected from the group consisting of a) Pyridachlometyl, b) N eth¬yl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]butanamide, c) N-ethyl-2-[(3-ethynyl-8 methyl-6 quinolyl)oxy]-2-methylsulfanyl-acetamide, d) 2-[(3-ethynyl-8-methyl-6-quinol¬yl)oxy]-N (2-fluoroethyl)butanamide, e) 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-flu¬oroeth¬yl)-2-methoxy-acetamide, f) 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-propyl-butanam¬ide, g) 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methoxy-N-propylacetamide, h) 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-N-propyl-acetamide, i) 2 [(3 ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methylsulfanyl-acetamide, and j) 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3 amine; B.7) Other compounds of unknown mode of action selected from the group consisting of a) diclocymet, b) fenitropan, c) harpin, d) picarbutrazox, e) dichlobentiazox, f) pyrifenamine, g) quinofumelin, h) ipflufenoquin, i) 4 cyclopropyl-N-(2,4-di¬methoxy¬phenyl)thiadiazole-5-carboxamide, j) N′-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]¬oxy]-2,5-dimethylphenyl]-N-ethyl-N-methyl-formamidine, k) N′-(5-bromo-6-indan-2-yl¬oxy-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine, l) N′-[5-bromo-6-[1-(3,5-diflu¬orophenyl)ethoxy]-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine, m) N′-[5-bromo-6-(4-isopropylcyclohexoxy)-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine, n) N′ [5 bromo-2-methyl-6-(1-phenylethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, o) ethyl (Z) 3 amino-2-cyano-3-phenyl-prop-2-enoate, p) pentyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxy¬methyl]-2-pyridyl]carbamate, q) but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)phenyl-methylene]amino]oxy¬methyl]-2-pyridyl]carbamate (picarbutrazox), r) 2-(6-benzyl-2-pyridyl)quinazoline, s) 2-[6-(3-fluoro-4 methoxy-phenyl)-5-methyl-2-pyridyl]quinazoline, and t) N′-(2,5-dimethyl-4-phen¬oxy-phenyl)-N-ethyl-N-methyl-formamidine, and B.8) N-[[2-fluoro-4-[(2S,3S)-2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl]methyl]cyclopropanecarboxamide; wherein component 1) and component 2) are present in a weight ratio of from 1000:1 to 1:1000.

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

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

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

5. The mixture of claim 1 comprising one compound B.

6. The mixture of claim 1 wherein component 2) is selected from compounds B.1 a) to B.1 n).

7. The mixture of claim 1 wherein component 2) is selected from compounds B.2 a) to B.2 c).

8. The mixture of claim 1 wherein component 2) is selected from compounds B.3.

9. The mixture of claim 1 wherein component 2) is selected from compounds B.4 a) and B.4 b).

10. The mixture of claim 1 wherein component 2) is selected from compounds of group B.5.

11. The mixture of claim 1 wherein component 2) is selected from compounds B.7 d), B.7 h), and B.7 t).

12. The mixture of claim 1 wherein component 2) is compound B.8.

13. A method for controlling phytopathogenic harmful fungi, comprising contacting the fungi, their habitat or the plants to be protected against fungal attack, the soil or seed are treated with an effective amount of a pesticidal mixture according to claim 1.

14. A method for protecting growing plants or plant propagation materials from attack or infestation by invertebrate pests, comprising 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 claim 1.

Description

EXAMPLES

[0093] The invention is now illustrated in further details by the following examples.

[0094] Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds. The presence of a synergistic effect in terms of percent control or efficiacy, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations Weeds, 15, 20-22):

[00001]$E=X+Y-\frac{\mathrm{XY}}{100}$

[0095] 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.

[0096] 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.

[0097] 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.

[0098] The following tests can demonstrate the control efficacy of mixtures or compositions of this invention on specific fungi. However, the pest control protection afforded by the compounds, mixtures or compositions is not limited to these species. In certain instances, combinations of a compound of this invention with other invertebrate pest control compounds or agents are found to exhibit synergistic effects against certain important invertebrate pests and/or harmful fungi.

[0099] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.

[0100] The product oxathiapiproline was used as commercial finished formulation and diluted with water to the stated concentration of the active compound.

[0101] 1. Activity Against the Late Blight Pathogen Phytophthora infestans in the Microtiter Test

[0102] 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 Phytophtora infestans containing a pea juice-based aqueous nutrient medium or 000 medium was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

TABLE-US-00001 Active compound/ Concentration Observed Calculated active mixture (ppm) Mixture efficacy efficacy (%) Synergism (%) Dimpropyridaz 0.063 — 4 0.016 — 0 Oxathiapiproline 0.063 — 11 B.5) a) 0.016 — 0 Dimpropyridaz 0.063 1:1 45 15 30 Oxathiapiproline 0.063 Dimpropyridaz 0.063 4:1 65 4 61 Oxathiapiproline 0.016 Dimpropyridaz 0.016 1:4 40 11 29 Oxathiapiproline 0.063

[0103] 2. Activity Against the Grey Mold Botrytis cinerea in the Microtiterplate Test

[0104] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

TABLE-US-00002 Active compound/ Concentration Observed Calculated active mixture (ppm) Mixture efficacy efficacy (%) Synergism (%) Dimpropyridaz 1 — 0 0.25 — 1 0.063 — 0 Pydiflumetofen B.2 a) 0.063 — 42 Isoflucypram B.2 f) 0.25 — 57 Pyrapropoyne B.2 d) 1 — 26 Dimpropyridaz 0.063 1:1 60 42 18 Pydiflumetofen 0.063 Dimpropyridaz 0.25 4:1 70 43 27 Pydiflumetofen 0.063 Dimpropyridaz 0.25 1:1 81 57 24 Isoflucypram 0.25 Dimpropyridaz 1 4:1 73 57 16 Isoflucypram 0.25 Dimpropyridaz 0.063 1:4 78 57 21 Isoflucypram 0.25 Dimpropyridaz 0.25 1:4 45 27 18 Pyrapropoyne 1

[0105] 3. Activity Against Leaf Blotch on Wheat Caused by Septoria tritici

[0106] 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 DOE solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

TABLE-US-00003 Active compound/ Concentration Observed Calculated active mixture (ppm) Mixture efficacy efficacy (%) Synergism (%) Dimpropyridaz 0.25 — 7 0.063 — 5 Isoflucypram 0.063 — 40 B.2) f) Dimpropyridaz 0.063 1:1 81 43 38 Isoflucypram 0.063 Dimpropyridaz 0.25 Isoflucypram 0.063 4:1 74 44 30

[0107] 4. Activity Against Cercospora Sojina in the Microtiter Test

[0108] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Cercospora sojina in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

TABLE-US-00004 Active compound/ Concentration Observed Calculated active mixture (ppm) Mixture efficacy efficacy (%) Synergism (%) Dimpropyridaz 63 — 23 0.25 — 0 Florylpicoxamid 16 — 61 B.3)a) 0.25 — 6 Dimpropyridaz 0.25 1:1 29 6 23 Florylpicoxamid 0.25 Dimpropyridaz 63 4:1 100 70 30 Florylpicoxamid 16

[0109] 5. Activity Against Colletotrichum orbiculare in the Microtiterplate Test

[0110] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Colletotricum orbiculare in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

TABLE-US-00005 Active compound/ Concentration Observed Calculated active mixture (ppm) Mixture efficacy efficacy (%) Synergism (%) Dimpropyridaz 63 — 14 Pydiflumetofen B.1) a) 16 — 59 Dimpropyridaz 63 4:1 96 65 31 Pydiflumetofen 16

[0111] 6. Activity Against Rhynchosporium secalis in the Microtiterplate Test

[0112] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Rhynchosporium secalis in an aqueous biomalt or yeast-bactopeptone-glycerine or DOE solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

TABLE-US-00006 Active compound/ Concentration Observed Calculated active mixture (ppm) Mixture efficacy efficacy (%) Synergism (%) Dimpropyridaz 63 — 12 B.5)d) 63 — 70 Dimpropyridaz 63 1:1 92 74 18 B.5)d) 63

[0113] 7. Activity Against Sclerotinia sclerotiorum in the Microtiterplate Test

[0114] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Sclerotinia sclerotiorum in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

TABLE-US-00007 Active compound/ Concentration Observed Calculated active mixture (ppm) Mixture efficacy efficacy (%) Synergism (%) Dimpropyridaz 0.25 — 0 Pyrapropoyne B.1)d) 1 — 27 Dimpropyridaz 0.25 1:4 48 27 21 Pyrapropoyne 1