Pesticidal Active Mixtures Comprising Isoxazoline Compounds I

Abstract

The present invention relates to pesticidal mixtures comprising as active compounds 1) at least one isoaxazoline compound I of the formula (I)

##STR00001## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and A are defined in the description; and 2) at least one active compound II selected from a group A comprising acteylcholine esterase inhibitors, GABA-gated chloride channel antagonists, sodium channel modulators, nicotinic acteylcholine receptor agonists/antagonists, chloride channel activators, juvenile hormone mimics, compounds affecting the oxidative phosphorylation, inhibitors of the chitin biosynthesis, moulting disruptors, inhibitors of the MET, voltage-dependent sodium channel blockers, inhibitors of the lipid synthesis and 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 in and on plants, and for protecting such plants being infested with pests, especially also for protecting plant propagation material as like seeds.

Claims

1-20. (canceled)

21. A pesticidal mixture comprising 1) at least one isoxazoline compound I of formula ##STR00017## or a salt thereof, and 2) at least one active compound II selected from the group consisting of allethrin, bifenthrin, beta-cyfluthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, tau-fluvalinate, metofluthrin, permethrin, profluthrin, pyrethrin (pyrethrum), silafluofen, and tralomethrin; wherein compound I and compound II are present in a weight ratio of from 500:1 to 1:100.

22. The mixture according to claim 21, wherein compound I is the compound of formula: ##STR00018## or a salt thereof.

23. The mixture according to claim 21, wherein compound I is the compound of formula: ##STR00019## or a salt thereof.

24. The mixture according to claim 21, wherein the active compound I and the active compound II are present in a weight ratio of 20:1 to 1:50.

25. The mixture according to claim 24, wherein the active compound I and the active compound II are present in a weight ratio of 5:1 to 1:20.

26. The mixture according to claim 21, wherein at least one active compound II is allethrin, bifenthrin, beta-cyfluthrin, or cyfluthrin.

27. The mixture according to claim 21, wherein at least one active compound II is lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, or zeta-cypermethrin.

28. The mixture of claim 21, wherein at least one active compound II is deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, or tau-fluvalinate.

29. The mixture of claim 21, wherein at least one active compound II is metofluthrin, permethrin, profluthrin, pyrethrin (pyrethrum), silafluofen, or tralomethrin

30. The mixture of claim 21, comprising one compound I.

31. The mixture of claim 30, wherein the compound I is compound C.I.240.

32. The mixture of claim 30, wherein the compound I is compound C.I.456.

33. The mixture of claim 30, comprising one compound II.

34. 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 21 in pesticidally effective amounts.

35. 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 21 in pesticidally effective amounts.

36. The method as claimed in claim 34, wherein the mixture is applied in an amount of from 5 g/ha to 2000 g/ha.

37. A method for protection of plant propagation material comprising contacting the plant propagation material with a mixture of claim 21 in pesticidally effective amounts.

38. A method according to claim 37 wherein the mixture is applied in an amount of from 0.1 g to 10 kg per 100 kg of plant propagation material.

39. A method as claimed in claim 37, wherein the plant propagation material is/are seed(s).

40. The method of claim 39, wherein the mixture is applied in an amount of from 0.1 g to 10 kg per 100 kg of seeds.

41. A method for protecting animals against infestation or infection by parasites which comprises administering to the animals a parasitically effective amount of a mixture according to claim 21 to the animal in need thereof.

42. A method for treating animals infested or infected by parasites which comprises administering to the animals a parasitically effective amount of a mixture according claim 21 to the animal in need thereof.

43. A method of claim 34 wherein the active compounds I of formula I and the active compounds II are applied simultaneously, that is jointly or separately, or in succession.

44. A pesticidal or parasiticidal composition, comprising a liquid or solid carrier and a mixture according to claim 21.

Description

EXAMPLES

[0390] Some of the preferred compound I examples are characterized by their physical data in the following table C.I.2. The characterization can be done by coupled High Performance Liquid Chromatography/mass spectrometry (HPLC/MS), by NMR or by their melting points.

[0391] The compounds were characterized by .sup.1H-NMR. The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: M=multiplett, q=quartett, t=triplett, d=doublet and s=singulett.

[0392] The compounds were also characterized by HPLC/MS. Analytical HPLC column: RP-18 column Chromolith Speed ROD from Merck KgaA, Germany). Elution: acetonitrile+0.1% trifluoroacetic acid (TFA)/water+0.1% trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 5 minutes at 40° C.

[0393] Physical data of some specific compound examples of isoxazoline compounds of formula I:

TABLE-US-00003 TABLE C.I.2 HPLC-MS .sup.1H-NMR Compound (t.sub.r = reten- (in CDCl.sub.3): example Structure of compound I tion time) δ [ppm] C.I.73 [00011] t.sub.r = 3.32 min; m = 494.0 .sup.1H-NMR (500 MHz, CDCl.sub.3): □ = 8.50 (d, 1H), 7.95 (m, 1H), 7.90 (m, 2H), 7.70 (m, 3H), 7.52 (s, 2H), 7.40 (m, 1H), 7.35 (m, 1H), 7.25 (m, 1H), 4.75 (s, 2H), 4.10 (d, 1H), 3.75 (m, 1H). C.I.235 [00012] t.sub.r = 3.40 min; m = 508.0 .sup.1H-NMR (500 MHz, CDCl.sub.3): □ = 8.55 (m, 1H), 7.70 (m, 1H), 7.50 (m, 5H), 7.45 (s, 1H), 7.40 (m, 1H), 7.25 (m, 2H), 4.75 (d, 2H), 4.05 (d, 1H), 3.68 (d, 1H), 2.50 (s, 3H). C.I.240 [00013] t.sub.r = 3.911 min; m = 556.1 .sup.1H-NMR (500 MHz, CDCl.sub.3): □ = 7.42-7.58 (m, 6H), 7.01 (br dd, 1H), 6.77 (br. dd, 1H), 4.20 (d, 2H), 4.08 (d, 1H), 3.95 (m, 1H), 3.71 (d, 1H), 2.44 (s, 3H). C.I.397 [00014] t.sub.r = 3.59 min; m = 544.1 .sup.1H-NMR (500 MHz, CDCl.sub.3): □ = 8.85 (m, 1H), 8.52 (m, 1H), 8.47 (m. 1H), 7.30-7.80 (m, 10H), 7.25 (m, 1H), 4.85 (m, 2H), 4.26 (d, 1H), 3.88 (d, 1H).

[0394] Biology

[0395] 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.

[0396] 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):

[00001]$E=\frac{\mathrm{XY}}{100}$

[0397] When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.

[0398] The following tests can 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.

[0399] Test B.1 Control of Green Peach Aphid (Myzus persicae)

[0400] For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.

[0401] The compounds or mixtures were formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures were pipetted into the aphid diet, using a custom built pipetter, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

[0402] After application, 5-8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at 23±1° C., 50±5% RH for 3 days. Aphid mortality and fecundity was then visually assessed. For the mixture tested the results are listed in table B.1.

TABLE-US-00004 TABLE B.1 Control of Green Peach Aphid (Myzus persicae) [00015] Green Peach Aphid ppm Average Control % Thiamethoxam + test compound C.I.240   0 + 2 0 0.4 + 0 25 0.4 + 2 100* Imidacloprid + test compound C.I.240   0 + 0.08 0 0.4 + 0 0   0.4 + 0.08 100* *synergistic control effect according to Colby's equation

[0403] Test B.2 Control of Boll Weevil (Anthonomus grandis)

[0404] For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 24-well-microtiter plates containing an insect diet and 20-30 A. grandis eggs. The compounds or mixtures were formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 20 μl, using a custom built micro atomizer, at two replications.

[0405] For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

[0406] After application, microtiter plates were incubated at 23±1° C., 50±5% RH for 5 days. Egg and larval mortality was then visually assessed. For the mixture tested the results are listed in table B.2.

TABLE-US-00005 TABLE B.2 Control of Boll Weevil (Anthonomus grandis) [00016] Average Boll Weevil ppm Control % Alpha-Cypermethrin + test compound C.I.240   0 + 0.4 50 0.08 + 0   0 0.08 + 0.4  100* Abamectin + test compound C.I.240   0 + 0.08 0 0.016 + 0    50 0.016 + 0.08  100* Flonicamid + test compound C.I.240   0 + 0.4 50 4 + 0 0   4 + 0.4 100* *synergistic control effect according to Colby's equation

[0407] In the following further test descriptions are given, which might also be used in order to evaluate the biological activity of the mixtures of the invention.

[0408] Test B.3

[0409] 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.

[0410] The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % 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.

[0411] For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

[0412] After application, the leaf disks are air-dried and 5-8 adult aphids are 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 (relative humidity) for 5 days. Aphid mortality and fecundity is then visually assessed.

[0413] Test B.4

[0414] 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. The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % 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.

[0415] For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

[0416] After application, microtiter plates are incubated at 28±1° C., 80±5% RH for 5 days. Egg and larval mortality is visually assessed.

[0417] Test B.5

[0418] 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.

[0419] The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % 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.

[0420] For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

[0421] After application, microtiter plates are incubated at 28±1° C., 80±5% RH for 5 days. Egg and larval mortality is visually assessed.

[0422] Test B.6

[0423] For evaluating 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.

[0424] The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % 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.

[0425] For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

[0426] 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 25±1° C., 80±5% RH for 3 to 5 days. Aphid mortality and fecundity is visually assessed.