Agricultural mixtures comprising carboxamide compound

Abstract

The present invention relates to agricultural mixtures comprising as active compound I a pesticidal active carboxamide and at least one fungicidal active compound II selected from azoles, strobilurins, carboxamides, carbamates, heterocyclic and various other compounds as defined in the description, in synergistically effective amounts. The invention relates further to methods and use of these mixtures for combating insects, arachnids or nematodes and harmful fungis in and on plants, and for protecting such plants being infested with pests, especially also for protecting seeds.

Claims

1. An agricultural mixture comprising as active compounds 1) one pesticidal active carboxamide compound I of formula (I): ##STR00002## or a tautomer, enantiomer, diastereomer or salt thereof, and 2) at least one fungicidal active compound II selected from the group consisting of fluxapyroxad, sedaxane, fluopyram, and penflufen; wherein the active compound I and the active compound II are present in synergistically effective amounts, and wherein the active compound I and the active compound II are present in a weight ratio of from 500:1 to 1:10.

2. The agricultural mixture of claim 1, wherein: the at least one active compound II is fluxapyroxad.

3. The agricultural mixture of claim 2, wherein the active compound I and the active compound II are present in a weight ratio of from 20:1 to 1:10.

4. The agricultural mixture of claim 1, wherein: the at least one active compound II is sedaxane.

5. The agricultural mixture of claim 4, wherein the active compound I and the active compound II are present in a weight ratio of from 20:1 to 1:10.

6. The agricultural mixture of claim 1, wherein: the at least one active compound II is fluopyram.

7. The agricultural mixture of claim 6, wherein the active compound I and the active compound II are present in a weight ratio of from 20:1 to 1:10.

8. The agricultural mixture of claim 1, wherein: the at least one active compound II is penflufen.

9. The agricultural mixture of claim 8, wherein the active compound I and the active compound II are present in a weight ratio of from 20:1 to 1:10.

10. Agricultural composition, comprising a liquid or solid carrier and a mixture according to claim 1.

11. A method for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or the soil or water in which the plant is growing, with a mixture according to claim 1 in pesticidally effective amounts.

12. A method for controlling insects, arachnids or nematodes comprising contacting an insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with a mixture according to claim 1 in pesticidally effective amounts.

13. A method for protection of plant propagation material comprising contacting the plant propagation material with a mixture as defined in claim 1 in pesticidally effective amounts.

14. Seed treated with the mixture according to claim 1 in an amount of from 0.1 g to 100 kg per 100 kg of seeds.

15. A method for controlling phytopathogenic harmful fungi, wherein the fungi, their habitat or the plants or the plant propagation material to be protected against fungal attack, the soil or seed are treated with a fungicidal effective amount of a mixture of at least one active compound I and at least one active compound II according to claim 1.

16. A method for protecting plants from phytopathogenic harmful fungi, wherein the fungi, their habitat or the plants or the plant propagation material to be protected against fungal attack, the soil or seed are treated with a fungicidal effective amount of a mixture of at least one active compound I and at least one active compound II according to claim 1.

Description

EXAMPLES

(1) B. Biology

(2) 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, 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):

(3) $E=X+Y-\frac{XY}{100}$

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

(5) The analysis of synergism or antagonism between the mixtures or compositions was determined using Colby's equation.

(6) B.1 Pesticidal Action Against Fungi

(7) Microtest for the Evaluation of Fungicidal Activity

(8) The active compounds were formulated separately as a stock solution having a concentration of 10,000 ppm in dimethyl sulfoxide.

(9) B.1.1. Activity Against Rice Blast Pyricularia oryzae

(10) The stock solutions were mixed according to the indicated ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18 C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The results are given in table B.1.1 hereinbelow.

(11) TABLE-US-00001 TABLE B.1.1. Pyricularia oryzae Active Calculated compound/ efficacy active Concen- according compounds tration Mixture Observed to Colby Synergism in mixture (ppm) (ratio) efficacy (%) (%) carboxamide 16 4 compound of 4 15 formula I 1 12 0.063 2 Epoxiconazol 0.25 28 0.063 1 carboxamide 16 64:1 100 31 69 compound of formula I Epoxiconazol 0.25 carboxamide 4 63:1 100 15 85 compound of formula I Epoxiconazol 0.063 carboxamide 4 16:1 100 39 61 compound of formula I Epoxiconazol 0.25 carboxamide 1 16:1 100 13 87 compound of formula I Epoxiconazol 0.063
B.1.2. Activity Against Leaf Blotch on Wheat Caused by Septoria tritici

(12) The stock solutions were mixed according to the indicated ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18 C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The results are given in table B.1.2 hereinbelow.

(13) TABLE-US-00002 TABLE B.1.2. Septoria tritici Active Calculated compound/ efficacy active Concen- according compounds tration Mixture Observed to Colby Synergism in mixture (ppm) (ratio) efficacy (%) (%) carboxamide 63 11 compound of formula I Epoxiconazol 0.016 7 Metalaxyl 4 5 1 5 Triticonazol 0.063 5 carboxamide 63 4000:1 49 18 31 compound of formula I Epoxiconazol 0.016 carboxamide 63 16:1 45 15 30 compound of formula I Metalaxyl 4 carboxamide 63 63:1 40 15 25 compound of formula I Metalaxyl 1 carboxamide 63 1000:1 42 16 26 compound of formula I Triticonazol 0.063
B.1.3. Activity Against Early Blight Caused by Alternaria solani

(14) The stock solutions were mixed according to the indicated ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Alternaria solani in an aqueous biomalt or yeast-bactopeptone-glycerine 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. The results are given in table B.1.3 hereinbelow.

(15) TABLE-US-00003 TABLE B.1.3. Alternaria solani Active Calculated compound/ efficacy active Concen- according compounds tration Mixture Observed to Colby Synergism in mixture (ppm) (ratio) efficacy (%) (%) carboxamide 63 0 compound of 16 0 formula I 4 0 1 0 Pyraclostrobin 0.063 12 0.016 0 Triticonazol 1 23 0.25 0 carboxamide 16 254:1 36 12 24 compound of formula I Pyraclostrobin 0.063 carboxamide 63 1000:1 40 12 28 compound of formula I Pyraclostrobin 0.063 carboxamide 63 4000:1 24 0 24 compound of formula I Pyraclostrobin 0.016 carboxamide 63 63:1 43 23 20 compound of formula I Triticonazol 1 carboxamide 16 64:1 32 0 32 compound of formula I Triticonazol 0.25 carboxamide 4 16:1 20 0 20 compound of formula I Triticonazol 0.25 carboxamide 4 4:1 52 23 29 compound of formula I Triticonazol 1 carboxamide 1 4:1 34 0 34 compound of formula I Triticonazol 0.25
B.1.4. Activity against wheat leaf spots caused by Leptosphaeria nodorum

(16) The stock solutions were mixed according to the indicated ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Leptosphaeria nodorum in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18 C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The results are given in table B.1.4 hereinbelow.

(17) TABLE-US-00004 TABLE B.1.4. Leptosphaeria nodorum Active Calculated compound/ efficacy active Concen- according compounds tration Mixture Observed to Colby Synergism in mixture (ppm) (ratio) efficacy (%) (%) carboxamide 4 1 compound of formula I Pyraclostrobin 0.25 72 carboxamide 4 16:1 100 72 28 compound of formula I Pyraclostrobin 0.25
B.1.5. Activity Against Microdochium nivale

(18) The stock solutions were mixed according to the indicated 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 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. The results are given in table B.1.5 hereinbelow.

(19) TABLE-US-00005 TABLE B.1.5. Microdochium nivale Active Calculated compound/ efficacy active Concen- according compounds tration Mixture Observed to Colby Synergism in mixture (ppm) (ratio) efficacy (%) (%) carboxamide 63 4 compound of 16 15 formula I 4 13 Pyraclostrobin 0.016 46 Fluxapyroxad 0.063 0 0.004 0 Epoxiconazol 0.016 29 0.004 8 carboxamide 4 250:1 79 53 26 compound of formula I Pyraclostrobin 0.016 carboxamide 16 1000:1 74 54 20 compound of formula I Pyraclostrobin 0.016 carboxamide 63 4000:1 93 48 45 compound of formula I Pyraclostrobin 0.016 carboxamide 63 1000:1 35 4 31 compound of formula I Fluxapyroxad 0.063 carboxamide 63 16000:1 25 4 21 compound of formula I Fluxapyroxad 0.004 carboxamide 4 250:1 63 38 25 compound of formula I Epoxiconazol 0.016 carboxamide 63 4000:1 99 31 68 compound of formula I Epoxiconazol 0.016 carboxamide 16 4000:1 99 21 78 compound of formula I Epoxiconazol 0.004

(20) B.1.6. Activity against Rhizoctonia solani

(21) The stock solutions were mixed according to the indicated ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Rhizoctonta solanlin an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18 C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The results are given in table B.1.6 hereinbelow.

(22) TABLE-US-00006 TABLE B.1.6. Rhizoctonia solani Active Calculated compound/ efficacy active Concen- according compounds tration Mixture Observed to Colby Synergism in mixture (ppm) (ratio) efficacy (%) (%) carboxamide 16 0 compound of 4 0 formula I 1 0 Epoxiconazol 0.016 24 0.004 0 0.001 0 Triticonazol 0.25 41 carboxamide 4 250:1 55 24 31 compound of formula I Epoxiconazol 0.016 carboxamide 63 4000:1 96 31 65 compound of formula I Epoxiconazol 0.016 carboxamide 16 4000:1 75 0 75 compound of formula I Epoxiconazol 0.004 carboxamide 4 4000:1 20 0 20 compound of formula I Epoxiconazol 0.001 carboxamide 1 63:1 44 24 20 compound of formula I Epoxiconazol 0.016 carboxamide 16 64:1 67 41 26 compound of formula I Triticonazol 0.25 carboxamide 4 16:1 67 41 26 compound of formula I Triticonazol 0.25 carboxamide 1 4:1 69 41 28 compound of formula I Triticonazol 0.25
B.1.7. Activity Against Pyrenophora teres

(23) The stock solutions were mixed according to the indicated ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Pyrenophora teres in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18 C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The results are given in table B.1.7 hereinbelow.

(24) TABLE-US-00007 TABLE B.1.7. Pyrenophora teres Active Calculated compound/ efficacy active Concen- according compounds tration Mixture Observed to Colby Synergism in mixture (ppm) (ratio) efficacy (%) (%) carboxamide 63 20 compound of 16 0 formula I 4 0 Pyraclostrobin 0.016 34 Epoxiconazol 0.016 0 carboxamide 4 250:1 61 34 27 compound of formula I Pyraclostrobin 0.016 carboxamide 16 1000:1 67 34 33 compound of formula I Pyraclostrobin 0.016 carboxamide 63 4000:1 73 20 53 compound of formula I Epoxiconazol 0.016

(25) The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.

(26) These percentages were converted into efficacies.

(27) As mentioned above, 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.

(28) The following further test systems may also be used to demonstrate and evaluate the fungicidal action of compounds, mixtures or compositions of this invention on specific fungi. However, the fungicidal control protection afforded by the compounds, mixtures or compositions is not limited to these fungi. In certain instances, combinations of a compound of this invention with other fungicidal compounds or agents are found to exhibit synergistic effects against certain important fungi.

(29) If not otherwise specified and as described above, the active substances are formulated separately as a stock solution in dimethyl sulfoxide (DMSO) at a concentration of 10 000 ppm.

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

(31) Fungicidal Test Example B.1.8:

(32) Activity Against the Grey Mold Botrytis cinerea in the Microtiterplate Test

(33) The stock solutions are mixed according to the desired 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 solution is added. The plates are placed in a water vapor-saturated chamber at a temperature of 18 C. Using an absorption photometer, the MTPs are measured at 405 nm 7 days after the inoculation.

(34) Fungicidal test example B.1.9:

(35) Activity Against Septoria glycines in the Microtiterplate Test

(36) The stock solutions are mixed according to the desired ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria glycines in an aqueous biomalt solution is added. The plates are placed in a water vapor-saturated chamber at a temperature of 18 C. Using an absorption photometer, the MTPs are measured at 405 nm 7 days after the inoculation.

(37) Fungicidal test example B.1.10:

(38) Activity Against Colletotrichum truncatum in the Microtiterplate Test

(39) The stock solutions are mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Colleotrichum truncatum in an aqueous biomalt solution is added. The plates are placed in a water vapor-saturated chamber at a temperature of 18 C. Using an absorption photometer, the MTPs are measured at 405 nm 7 days after the inoculation.

(40) Fungicidal Test Example B.1.11

(41) Fungicidal Control of Brown Spot Caused by Cochliobolus miyabeanus (Protective)

(42) Leaves of pot-grown rice seedlings are sprayed to run-off with an aqueous suspension containing a certain concentration of active ingredients prepared from a stock solution. The plants are allowed to air-dry. At the following day the plants are inoculated with an aqueous spore suspension of Cochliobolus miyabeanus. Then the trial plants are immediately to be transferred to a humid chamber. After 6 days at 22-24 C. and a relative humidity close to 100% the extent of fungal attack on the leaves is visually assessed as % diseased leaf area.

(43) Also here, the measured parameters of the fungicidal tests are to be compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages are to be 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 are not growing.

(44) B.2 Pesticidal Activity Against Animal Pests

(45) The following tests can further demonstrate the control efficacy of compounds, mixtures or compositions of this invention on specific animal 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.

(46) Insecticidal Test Example B.2.1:

(47) For evaluating e.g. the control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consists of 24-well-microtiter plates containing broad bean leaf disks.

(48) The compounds or mixtures are formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the leaf disks at 2.5 l, using a custom built micro atomizer, at two replications.

(49) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

(50) After application, the leaf disks are air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids are then allowed to suck on the treated leaf disks and incubated at about 231 C. and about 505% RH (relative humidity) for 5 days. Aphid mortality and fecundity is visually assessed.

(51) Insecticidal Test Example B.2.2:

(52) For evaluating e.g. the control of bird cherry aphid (Rhopalosiphum padi) through contact or systemic means the test unit consists of 96-well-microtiter plates containing barley leaf disks.

(53) The compounds or mixtures are formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the leaf disks at 2.5 l, using a custom built micro atomizer, at two replications.

(54) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

(55) After application, the leaf disks are air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids are then allowed to suck on the treated leaf disks and incubated at about 251 C. and about 805% RH for 3 to 5 days. Aphid mortality and fecundity is visually assessed.

(56) Insecticidal Test Example B.2.3:

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

(58) The compounds or mixtures are formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures are pipetted into the aphid diet, using a custom built pipetter, at two replications.

(59) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

(60) After application, 5-8 adult aphids are placed on the artificial membrane inside the microtiter plate wells. The aphids are then allowed to suck on the treated aphid diet and incubated at about 231 C. and about 505% RH for 3 days. Aphid mortality and fecundity is visually assessed.

(61) Insecticidal Test Example B.2.4:

(62) For evaluating e.g. control of boll weevil (Anthonomus grandis) the test unit consists of 24-well-microtiter plates containing an insect diet and 20-30 A. grandis eggs.

(63) The compounds or mixtures are formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the insect diet at 20 l, using a custom built micro atomizer, at two replications.

(64) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

(65) After application, microtiter plates are incubated at about 231 C. and about 505% RH for 5 days. Egg and larval mortality is visually assessed.

(66) Insecticidal Test Example B.2.5:

(67) For evaluating e.g. control of Mediterranean fruitfly (Ceratitis capitata) the test unit consists of 96-well-microtiter plates containing an insect diet and 50-80 C. capitata eggs.

(68) The compounds or mixtures arre formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the insect diet at 5 l, using a custom built micro atomizer, at two replications.

(69) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

(70) After application, microtiter plates are incubated at about 281 C. and about 805% RH for 5 days. Egg and larval mortality is then visually assessed.

(71) Insecticidal Test Example B.2.6:

(72) For evaluating e.g. control of tobacco budworm (Heliothis virescens) the test unit consists of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.

(73) The compounds or mixtures are formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the insect diet at 10 l, using a custom built micro atomizer, at two replications.

(74) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

(75) After application, microtiter plates are incubated at about 281 C. and about 805% RH for 5 days. Egg and larval mortality is visually assessed.