Pesticidal Mixtures

Abstract

The present invention relates to mixtures comprising, as active components, 1) an insecticidal compound I selected from fipronil and ethiprole; and 2) a fungicidal compound IIA selected from azoles, strobilurins, carboxamides, heterocylic compounds, carbamates, and other active compounds, and optionally 3) one or two fungicidal compounds IIB selected from List B which is defined as List A plus triticonazole, orysastrobin, in synergistically effective amounts, all as further defined in the description.

Claims

1. (canceled)

2. A fungicidal mixture comprising a fungicidal compound IIB selected from the group consisting of: difenoconazole, bitertanole, bromuconazole, diniconazole, enilconazole, fenbuconazole, flusilazole, fluquinconazole, flutriafol, imibenconazole, ipconazole, myclobutanil, paclobutrazol, penconazole, propiconazole, simeconazole, tetraconazole, uniconazole-P, triadimenol, triadimefon, triticonazole, cyazofamid, pefurazoate, benomyl, carbendazim, fuberidazole, thiabendazole, ethaboxam, etridiazole, hymexazole, cyproconazole, epoxiconazole, hexaconazole, metconazole, prothioconazole, and tebuconazole; a fungicidal compound IID selected from the group consisting of pyraclostrobin, and strobilurins selected from the group consisting of: azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, trifloxystrobin, or methyl (2-chloro-5-[1-(3 -methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1-(6-methylpyridin-2-yl-methoxyimino)ethyl]benzyl)carbamate, and methyl 2-(ortho-((2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate; and thiophanate-methyl in synergistically effective amounts.

3. The fungicidal mixture of claim 2, wherein the compound IID is selected from the group consisting of pyraclostrobin, azoxystrobin, picoxystrobin, and trifloxystrobin.

4. The fungicidal mixture of claim 2, wherein compound IIB is selected from the group consisting of difenoconazole, cyproconazole, epoxiconazole, fenbuconazole, fluquinconazole, flutriafol, ipconazole, metconazole, propiconazole, prothioconazole, tebuconazole, triadimenol, triticonazole, imazalil, prochloraz, carbendazim, thiabendazole, ethaboxam, and hymexazole; and wherein compound BD is pyraclostrobin.

5. The fungicidal mixture of claim 2, wherein compound IIB is selected from the group consisting of difenoconazole, cyproconazole, epoxiconazole, fluquinconazole, ipconazole, metconazole, prothioconazole, tebuconazole, triticonazole, and prochloraz; and wherein compound IID is pyraclostrobin.

6. The fungicidal mixture of claim 2, wherein compound IIB is selected from the group consisting of epoxiconazole, ipconazole, metconazole, prothioconazole, and triticonazole; and wherein compound IID is pyraclostrobin.

7. The fungicidal mixture of claim 2, wherein compound IIB is selected from the group consisting of metconazole, prothioconazole, and triticonazole; and wherein compound BD is pyraclostrobin

8. The fungicidal mixture of claim 2, wherein compound IIB is triticonazole and IID is pyraclostrobin.

9. The fungicidal mixture of claim 2, comprising thiophanate-methyl, compound IIB, and the compound IID in a weight ratio of from 1:200:200 to 200:1:1.

10. The fungicidal mixture of claim 2, comprising thiophanate-methyl, compound IIB, and the compound IID in a weight ratio of from 1:100:100 to 100:1:1.

11. The fungicidal mixture of claim 2, comprising thiophanate-methyl, compound IIB, and the compound IID in a weight ratio of from 10:20:20 to 20:1:1.

12. A pesticidal composition, comprising a liquid or solid carrier and the mixture of claim 2.

13. A method for controlling phytopathogenic harmful fungi, wherein the fungi, their habitat or the plants to be protected against fungal attack, the soil or seed are treated with an effective amount of the mixture of claim 2.

14. The method of claim 13, wherein the mixture is applied in an amount of from 5 g/ha to 2000 g/ha.

15. A method for protection of seeds comprising contacting the seeds with the mixture of claim 2 in pesticidally effective amounts.

16. The method of claim 15, wherein the mixture is applied in an amount of from 0.1 g to 10 kg per 100 kg of seeds.

17. The method of claim 13, wherein the compounds of the mixture are applied simultaneously, that is jointly or separately, or in succession.

18. A seed comprising the mixture of claim 2 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.

19. The fungicidal mixture of claim 2, wherein the mixture consists of thiophanate-methyl, triticonazole and pyraclostrobin.

Description

BIOLOGICAL EXAMPLES

[0662] 1) Fungicidal Action

[0663] The fungicidal effect of the compound and the mixtures could be demonstrated by the following tests:

[0664] The active compounds, separately or jointly, were prepared as a stock solution comprising 0.25% by weight of active compound in acetone or DMSO. 1% by weight of the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersant action based on ethoxylated alkylphenols) was added to this solution, and the mixture was diluted with water to the desired concentration.

[0665] The visually determined percentages of infected leaf areas were converted into efficacies in % of the untreated control:

[0666] The efficacy (E) is calculated as follows using Abbots formula:

E=(1−α/β).Math.100 [0667] α corresponds to the fungicidal infection of the treated plants in % and [0668] β corresponds to the fungicidal infection of the untreated (control) plants in %

[0669] An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.

[0670] The expected efficacies of mixtures of active compounds were determined using Colby's formula (Colby, S. R. “Calculating synergistic and antagonistic responses of herbicide Combinations”, Weeds, 15, 20-22, 1967) and compared with the observed efficacies.

[0671] Colby's formula:

E=x+y−x.Math.y/100 [0672] E expected efficacy, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b [0673] x efficacy, expressed in % of the untreated control, when using the active compound A at the concentration a [0674] y efficacy, expressed in % of the untreated control, when using the active compound B at the concentration b

Use Example 1

Fungicidal Control of Brown Spot Caused by Cochliobolus Miyabeanus (Protective)

[0675] Leaves of pot-grown rice seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient as described below prepared from the stock solution. The plants were allowed to air-dry. At the following day the plants were inoculated with an aqueous spore suspension of Cochliobolus miyabeanus. Then the trial plants were immediately 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 was visually assessed as % diseased leaf area.

[0676] The test results show that, by virtue of strong synergism, the activity of the mixtures according to the invention is considerably higher than had been predicted using Colby's formula.

[0677] 2) Action Against Animal Pests

[0678] The following tests demonstrate the control efficacy of compounds, mixtures or compositions of this invention on specific pests. However, the pest control protection afforded by the compounds, mixtures or compositions is not limited to these species. In certain instances, combinations of a compound of this invention with other invertebrate pest control compounds or agents are found to exhibit synergistic effects against certain important invertebrate pests.

[0679] The analysis of synergism or antagonism between the mixtures or compositions is determined using Colby's equation.

Use Example 2

[0680] For evaluating 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.

[0681] 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 μl, using a custom built micro atomizer, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

[0682] 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 23±1° C., 50±5% RH (room humidity) for 5 days. Aphid mortality and fecundity is visually assessed.

Use Example 3

[0683] For evaluating 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.

[0684] 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 μl, using a custom built micro atomizer, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

[0685] After application, microtiter plates are incubated at 23±1° C., 50±5% RH for 5 days. Egg and larval mortality is visually assessed.

Use Example 4

[0686] For evaluating 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.

[0687] 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 5 μl, using a custom built micro atomizer, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

[0688] After application, microtiter plates are incubated at 28±1° C., 80±5% RH for 5 days. Egg and larval mortality is visually assessed.

Use Example 5

[0689] For evaluating 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.

[0690] 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 μl, using a custom built micro atomizer, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

[0691] After application, microtiter plates are incubated at 28±1° C., 80±5% RH for 5 days. Egg and larval mortality is visually assessed.

[0692] In the following examples 6 and 7, the active ingredients were formulated separately as stock solutions at a concentration of 10 000 ppm in DMSO. The active ingredient pyraclostrobin was employed as a commercially available formulation.

Use Example No. 6

Activity Against the Causative Agent of Gray Mold Botrytis Cinerea in the Microtiter Test (Botrci)

[0693] The stock solution was pipetted into a microtiter plate (MTP) and diluted to the stated active ingredient concentration with an aqueous malt-based medium for fungi. An aqueous spore suspension of Botrytis cinerea was subsequently added. The plates were placed into a water-vapor-saturated chamber at temperatures of 18° C. On day 7 post-inoculation, the MTPs were measured at 405 nm using an absorption photometer.

[0694] The parameters measured were related to the growth of the control variant, which was free from active ingredients, and the blank, which was free from fungi and active ingredients, in order to determine the relative growth % of the pathogens in the individual active ingredients.

[0695] The visually determined data for the affected leaf area in % was first averaged and then converted into efficacies as % of the untreated control. An efficacy of 0 is the same disease level as in the untreated control, an efficacy of 100 is 0% disease level. The expected efficacies for active ingredient combinations were determined using Colby's formula (Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide Combinations”, Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.

TABLE-US-00004 Activity calculated using Observed Col- Active ingredient/a.i. Concentration activity by's formula Synergistic combination (ppm) Ratio (%) (%) effect in (%) pyraclostrobin 0.016  4 triticonazole + 0.063 + 0.25 12 thiophanate-methyl pyraclostrobin 0.016 + 0.063 + 0.25 1:4:16 35 15 20 triticonazole + thiophanate-methyl

Use Example No. 7

Activity Against the Causative Agent of Rice Blast Disease Pyricularia Oryzae in the Microtiter Test (Pyrior)

[0696] The stock solution was pipetted into a microtiter plate (MTP) and diluted to the stated active ingredient concentration with an aqueous malt-based medium for fungi. An aqueous spore suspension of Pyricularia oryzae was subsequently added. The plates were placed into a water-vapor-saturated chamber at temperatures of 18° C. On day 7 post-inoculation, the MTPs were measured at 405 nm using an absorption photometer.

[0697] The parameters measured were related to the growth of the control variant, which was free from active ingredients, and the blank, which was free from fungi and active ingredients, in order to determine the relative growth % of the pathogens in the individual active ingredients.

[0698] The visually determined data for the affected leaf area in % was first averaged and then converted into efficacies as % of the untreated control. An efficacy of 0 is the same disease level as in the untreated control, an efficacy of 100 is 0% disease level. The expected efficacies for active ingredient combinations were determined using Colby's formula (Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide Combinations”, Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.

TABLE-US-00005 Activity calculated Observed using Col- Active ingredient/a.i. Concentration activity by's formula Synergistic combination (ppm) Ratio (%) (%) effect in (%) pyraclostrobin 0.001 31 triticonazole + 0.004 + 0.016  5 thiophanate-methyl pyraclostrobin 0.001 + 0.004 + 0.016 1:4:16 60 35 25 triticonazole + thiophanate-methyl

Use Example No. 8

Activity Against the Causative Agent of Rice Blast Disease Pyricularia Oryzae in the Microtiter Test (Pyrior)

[0699] The active ingredients were formulated separately as stock solutions at a concentration of 10 000 ppm in DMSO.

[0700] The stock solution was pipetted into a microtiter plate (MTP) and diluted to the stated active ingredient concentration with an aqueous malt-based medium for fungi. An aqueous spore suspension of Pyricularia olyzae was subsequently added. The plates were placed into a water-vapor-saturated chamber at temperatures of 18° C. On day 7 post-inoculation, the MTPs were measured at 405 nm using an absorption photometer.

[0701] The parameters measured were related to the growth of the control variant, which was free from active ingredients, and the blank, which was free from fungi and active ingredients, in order to determine the relative growth % of the pathogens in the individual active ingredients.

[0702] The visually determined data for the affected leaf area in % was first averaged and then converted into efficacies as % of the untreated control. An efficacy of 0 is the same disease level as in the untreated control; an efficacy of 100 is 0% disease level. The expected efficacies for active ingredient combinations were determined using Colby's formula (Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide Combinations”, Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.

TABLE-US-00006 Activity calculated Observed using Col- Active ingredient/a.i. Concentration activity by's formula Synergistic combination (ppm) Ratio (%) (%) effect in (%) triticonazole + 2 + 2 22 clothianidin fipronil 2 5 triticonazole + 2 + 2 + 2 1:1:1 61 26 35 clothianidin + fipronil