Pesticidal Mixtures Comprising A Pyrazole Compound

Abstract

Pesticidal mixtures comprising as active compounds

1) at least one pyrazole compound A of formula I:

##STR00001##

wherein the variables are as defined in the specification, and
2) at least one further compound B selected from 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide; 4-[(5S)-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide; N-[4-Chloro-3-[[(phenylmethyl)-amino]-carbonyl]-phenyl]-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide; N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide; N-[4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide; 2-chloro-N-(1-cyanocy-clopropyl)-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide; 2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(3-ethylsulfonyl-2-pyridyl)-5-(trifluoromethylsulfonyl)-1,3-benzoxazole; spiropidion, acynonapyr, and benzpyrimoxan; methods and use of these mixtures for combating invertebrate pests such as 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

1-16. (canceled)

17. A pesticidal mixture comprising as active components 1) at least one pyrazole compound A of formula I: ##STR00005## wherein R.sup.1 is H, CH.sub.3, or C.sub.2H.sub.5; R.sup.2 is CH.sub.3, R.sup.3 is CH.sub.3, CH(CH.sub.3).sub.2, CF.sub.3, CHFCH.sub.3, or 1-CN-c-C.sub.3H4; R.sup.4 is CH.sub.3; or R.sup.3 and R.sup.4 may together form CH.sub.2CH.sub.2CF.sub.2CH.sub.2CH.sub.2; and 2) at least one further compound B selected from the group consisting of B1) an isoxazoline selected from the group consisting of a) 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin- 4-yl]-2-methyl-benzamide, and b) 4-[(5S)-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-31-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl- benzamide; B2) a carboxamide selected from the group consisting of a) N-[4-Chloro-3-[[(phenylmethyl)-amino]-carbonyl]-phenyl]-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-4- (trifluoromethyl)-1H-pyrazole-5-carboxamide; b) N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3- carboxamide; c) N-[4-chloro-3-[(1-cyanocyclopropyl)carb-amoyl]phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carb-oxamide; and d) 2- chloro-N-(1-cyanocyclopropyl)-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide; B3) a pyridylsulfone selected from the group consisting of a) 2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethypimidazo[4,5-b]pyridine, and b) 2-(3- thylsulfonyl-2-pyridyl)-5-(trifluoromethylsulfonyl)-1,3-benzoxazole; B4) Spiropidion; B5) Acynonapyr; and B6) Benzpyrimoxan; wherein component 1) and component 2) are present in a weight ratio of from 1000:1 to 1:1000.

18. The mixture of claim 17, wherein compound A is selected from the group consisting of: compound (I-1): 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, compound (I-2): 1-[1-(1-cyanocyclopropypethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, and compound (I-3): N-ethyl-1-(2-fluoro-1-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide.

19. The mixture of claim 17 comprising one compound A and one compound B.

20. The mixture of claim 17 wherein component 2) is selected from the group consisting of compounds B1 a) and B1 b).

21. The mixture of claim 17 wherein component 2) is selected from the group consisting of compounds B2 a) to B2 d).

22. The mixture of claim 17 wherein component 2) is selected from the group consisting of compounds B3 a) and B3b).

23. The mixture of claim 17, comprising the pyrazole compound A and the active compound B in a weight ratio of from 20:1 to 1:20.

24. A composition comprising a pesticidal mixture of claim 17 and at least one inert liquid and/or solid carrier.

25. An agricultural composition for combating animal pests comprising a pesticidal mixture of claim 17 and at least one inert liquid and/or solid acceptable carrier and, if desired, at least one surfactant.

26. A method for combating or controlling invertebrate pests, which method comprises contacting said pests or its food supply, habitat or breeding grounds with a pesticidally effective amount of a pesticidal mixture of claim 17.

27. The method of claim 26, wherein the pests are selected from the group consisting of the families of Pentatomidae, Cicadellidae, and Aphididae.

28. A method for protecting growing plants or plant propagation materials from attack or infestation by invertebrate pests, which method comprises 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 of claim 17.

29. Plant propagation material comprising a pesticidal mixture of claim 17 in an amount of from 0.1 g to 10 kg per 100 kg of plant propagation material.

30. A method for protection of plant propagation material comprising contacting the plant propagation material with a pesticidal mixture of claim 17 in an amount of from 0.1 g to 10 kg per 100 kg of plant propagation material.

31. The mixture of claim 18 comprising one compound A and one compound B.

32. The mixture of claim 18 wherein component 2) is selected from the group consisting of compounds B1 a) and B1 b).

33. The mixture of claim 18 wherein component 2) is selected from the group consisting of compounds B2 a) to B2 d).

34. The mixture of claim 18 wherein component 2) is selected from the group consisting of compounds B3 a) and B3b).

35. The mixture of claim 18, comprising the pyrazole compound A and the active compound B in a weight ratio of from 20:1 to 1:20.

36. A composition comprising a pesticidal mixture of claim 18 and at least one inert liquid and/or solid carrier.

Description

EXAMPLES

[0454] The present invention is now illustrated in further details by the following examples.

[0455] 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]$E=X+Y-\frac{\mathrm{XY}}{1.Math.0.Math.0}$

[0456] When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.

[0457] The following tests can demonstrate the control efficacy of mixtures or compositions of this invention on specific pests and 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.

[0458] 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.

Biological Examples of the Invention

[0459] If not otherwise specified, the test solutions are prepared as follows:

[0460] The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water : acteone. The test solution is prepared at the day of use.

[0461] Test solutions are prepared in general at concentrations of 1000 ppm, 500 ppm, 300 ppm, 100 ppm and 30 ppm (wt/vol).

Test 1

[0462] For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks. The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the leaf disks at 2.5 l, 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, were mixed together.

[0463] After application, the leaf disks were air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at 231 C., 505% RH for 5 days. Aphid mortality and fecundity was then visually assessed.

Test 2

[0464] For evaluating control of Caenorhaboiltis elegans through contact or systemic means the test unit consisted of 96-well-microtiter plates containing a liquid diet.

[0465] The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed into the microtiter plate wells at 5 l per well, using a custom built micro atomizer, at two replications. Mixed instar 60-100 C. elegans were transferred into the microtiter plate wells. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

[0466] After application, the nematodes were incubated at 181 C., 705% RH for 4 days. Nematode motility (mortality) was then visually assessed.

Test 3

[0467] For evaluating control of green peach aphid (Myzus perslcae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane. The compounds or mixtures were formulated using a solution containing 75% water and 25% 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.

[0468] 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 231 C., 505% RH for 3 days. Aphid mortality and fecundity was then visually assessed.

Test 4

[0469] 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% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 20 l, 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, were mixed together.

[0470] After application, microtiter plates were incubated at 231 C., 505% RH for 5 days. Egg and larval mortality was then visually assessed.

Test 5

[0471] For evaluating control of Mediterranean fruitfly (Ceratitis capitata) the test unit consisted of 96-well-microtiter plates containing an insect diet and 50-80 C capitata eggs.

[0472] The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 5 l, 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, were mixed together.

[0473] After application, microtiter plates were incubated at 281 C., 805% RH for 5 days. Egg and larval mortality was then visually assessed.

Test 6

[0474] For evaluating control of tobacco budworm (Hellothis virescens) the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.

[0475] The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 10 l, 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, were mixed together.

[0476] After application, microtiter plates were incubated at 281 C., 805% RH for 5 days. Egg and larval mortality was then visually assessed.

Test 7

[0477] For evaluating control of yellow fever mosquito (Aedes aegypti) the test unit consisted of 96-well-microtiter plates containing 200 l of tap water per well and 5-15 freshly hatched A. aegypti larvae.

[0478] The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5 l, 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, were mixed together.

[0479] After application, microtiter plates were incubated at 281 C., 805% RH for 2 days. Larval mortality was then visually assessed.

Test 8

[0480] For evaluating control of Greenhouse Whitefly (Trialeurodes vaporarlorum) the test unit consisted of 96-well-microtiter plates containing a leaf disk of egg plant leaf disk with white fly eggs. The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5 l, using a custom built micro atomizer, at two replications.

[0481] For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

[0482] After application, microtiter plates were incubated at 231 C., 655% RH for 6 days. Mortality of hatched crawlers was then visually assessed.