Active compound combinations having insecticidal/acaricidal properties

Abstract

The present invention relates to novel active compound combinations comprising at least one known compound of the formula (I) and at least one further active compound, which combinations are highly suitable for controlling animal and microbial pests such as unwanted insects and/or unwanted acarids and/or unwanted nematodes. ##STR00001##

Claims

1. An active compound combination comprising a compound of formula (I): ##STR00006## and at least one active agent of group (II), wherein the active agent is selected from the group consisting of: (II-1) methiocarb, (II-17) diafenthiuron, (II-18) acequinocyl, (II-19) fenazaquin, (II-20) fenpyroximate, (II-21) pyridaben, (II-22) tebufenpyrad, (II-24) fluopyram, (II-25) fluazaindolizine, (II-26) fluensulfone, (II-27) tioxazafen, (II-28) bifenazate, (II-31) a formulation comprising the three terpenes α-terpinene, p-cymene and limonene in a total amount of 15-18% (w/w) terpenes, a compound of formula (IIa): ##STR00007## a compound of formula (IIb): (1.34) Bacillus firmus, (2.54) Metarhizium anisopliae, (2.73) Paecilomyces lilacinus, and (7.24) natural extract or simulated blend of Chenopodium ambrosioides which contains a mixture of three terpenes; wherein the active compound combination is synergistically active.

2. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is selected from the group consisting of (II-1) Methiocarb, (II-17) diafenthiuron, (II-18) acequinocyl, (II-19) fenazaquin, (II-20) fenpyroximate, (II-21) pyridaben, (II-22) tebufenpyrad, (II-24) Fluopyram, (II-25) Fluazaindolizine, (II-26) Fluensulfone, (II-27) Tioxazafen, (II-28) Bifenazate, and (II-31) a formulation comprising a-terpinene, p-cymene and limonene in a total amount of 15- 18%.

3. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is selected from the group consisting of the compound of formula (IIa) and the compound of formula (IIb).

4. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is selected from the group consisting of (2.54) Metarhizium anisopliae, (2.73) Paecilomyces lilacinus, and (7.24) natural extract or simulated blend of Chenopodium ambrosioides which contains a mixture of three terpenes.

5. The active compound combination according to claim 1, wherein the compound of the formula (I) is present in form of its (+) enantiomer.

6. A method for controlling an animal pest, comprising allowing the active compound combination according to claim 1, to act on the animal pest and/or its habitat.

7. The method according to claim 6, wherein the animal pest is an insect or arachnid or acarid pest.

8. A method for controlling a microbial pest, comprising allowing the active compound combination according to claim 1, to act on the microbial pest and/or its habitat.

9. A method for controlling a nematode, comprising allowing the active compound combination according to claim 1, to act on the nematode and/or its habitat nematodes.

10. A method for plant-strengthening, comprising allowing the active compound combination according to claim 1, to act on the plant, its parts, and/or its surroundings, habitat, or storage space.

11. A method for seed treatment, comprising applying the active compound combination according to claim 1, to a seed.

12. A method for controlling an animal or a microbial pest, comprising allowing the active compound combination according to claim 1, to act on the animal or the microbial pest and/or its habitat.

13. The method according to claim 12, wherein the animal pest is an insect or arachnid or acarid pest.

14. A process for preparing a crop protection agent, comprising mixing the active compound combination according to claim 1, with an extender and/or a surfactant.

15. A method for treating a plant or parts thereof selected from the group consisting of citrus, pome fruits, stone fruits, tropical fruits, nuts, berries, vegetables, cotton, soybean, grape, tea, coffee, maize, rice, and ornamentals, comprising allowing the active compound combination according to claim 1, to act on the plant or parts thereof.

16. The method according to claim 10, wherein the plant is a transgenic plant.

17. The method according to claim 11, wherein the seed is a transgenic seed.

18. The active compound combination according to claim 1, wherein the compound of the formula (I) is present in form of a mixture of its (+) enantiomer and its (−) enantiomer which is enriched in the (+) enantiomer.

19. The active compound combination of claim 1, wherein: when the active agent of group (II) is (II-1) methiocarb, (II-17) diafenthiuron, (II-18) acequinocyl, (II-19) fenazaquin, (II-20) fenpyroximate, (II-21) pyridaben, (II-22) tebufenpyrad, (II-25) fluazaindolizine, (II-26) fluensulfone, (II-27) tioxazafen, (II-28) bifenazate, (II-31) a formulation comprising the three terpenes α-terpinene, p-cymene and limonene in a total amount of 15-18% (w/w) terpenes, a compound of formula (IIa), or a compound of formula (IIb), then the active compound combination has a ratio of the compound of formula (I) and the active agent of group (II) from 50:1 to 1:50 by weight; when the active agent of group (II) is (II-24) fluopyram, then the active compound combination has a ratio of the compound of formula (I) to (II-24) fluopyram from 250:1 to 1:10 by weight; when the active agent of group (II) is (1.34) Bacillus Firmus or (2.73) Paecilomyces lilacinus, then the active compound combination has a ratio of the compound of formula (I) and the active agent of group (II) from 5:1 to 1:10 by weight; when the active agent of group (II) is (2.54) Metarhizium anisopliae, then the active compound combination has a ratio of the compound of formula (I) and the active agent of group (II) from 5:1 to 1:10 by weight; when the active agent of group (II) is (7.24) natural extract or simulated blend of Chenopodium ambrosioides which contains a mixuture of three terpenes, then the active compound combination has a ratio of the compound of formula (I) and the active agent of group (II) from 10:1 to 1:30 by weight.

20. The active compound combination according to claim 19, wherein the compound of the formula (I) is present in form of its (+) enantiomer.

21. The active compound combination according to claim 19, wherein the compound of the formula (I) is present in form of a mixture of its (+) enantiomer and its (−) enantiomer which is enriched in the (+) enantiomer.

22. The active compound combination according to claim 21, wherein the compound of the formula (I) is present in the form of a mixture of its (+) enantiomer and its (−) enantiomer in a ratio of at least 60:40 (+):(−) enantiomer.

23. The active compound combination according to claim 1, wherein the compound of the formula (I) is present in the form of a mixture of its (+) enantiomer and its (−) enantiomer in a ratio of at least 60:40 (+):(−) enantiomer.

24. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (II-1) methiocarb.

25. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (II-17) diafenthiuron.

26. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (II-18) acequinocyl.

27. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (II-19) fenazaquin.

28. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (II-20) fenpyroximate.

29. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (II-21) pyridaben.

30. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (11-22) tebufenpyrad.

31. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (11-24) fluopyram.

32. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (11-25) fluazaindolizine.

33. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (11-26) fluensulfone.

34. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (II-27) tioxazafen.

35. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (II-28) bifenazate.

36. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (II-31) a formulation comprising the three terpenes α-terpinene, p-cymene and limonene in a total amount of 15-18% (w/w) terpenes.

37. The active compound combination according to claim 36, wherein the at least one active agent of group (II) is a formulation comprising α-terpinene, p-cymene and limonene in a total amount of 16.75% (w/w) terpenes.

38. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is the compound of formula (IIa).

39. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is a compound of formula (IIb).

40. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (1.34) Bacillus firmus.

41. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (2.54) Metarhizium anisopliae.

42. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (2.73) Paecilomyces lilacinus.

43. The active compound combination according to claim 1, wherein the at least one active agent of group (II) is (7.24) natural extract or simulated blend of Chenopodium ambrosioides which contains a mixture of three terpenes.

44. The active compound combination according to claim 43, wherein the natural extract or simulated blend of Chenopodium ambrosioides contains a mixture of α-terpinene, p-cymene and limonene.

Description

EXAMPLES

(1) Formula for the Efficacy of the Combination of Two Compounds

(2) The expected efficacy of a given combination of two compounds is calculated as follows (see Colby, S. R., “Calculating Synergistic and antagonistic Responses of Herbicide Combinations”, Weeds 15, pp. 20-22, 1967): If X is the efficacy expressed in % mortality of the untreated control for test compound A at a concentration of m ppm respectively m g/ha, Y is the efficacy expressed in % mortality of the untreated control for test compound B at a concentration of n ppm respectively n g/ha,

(3) E is the efficacy expressed in % mortality of the untreated control using the mixture of A and B at m and n ppm respectively m and n g/ha, then is

(4) $E=X+Y-\frac{X\times Y}{100}$ If the observed insecticidal efficacy of the combination is higher than the one calculated as “E”, then the combination of the two compounds is more than additive, i.e., there is a synergistic effect.

(5) In all following examples, “Bacillus firmus” refers to Bacillus firmus strain CNCM I-1582 unless indicated otherwise.

Example A

(6) Tetranychus urticae—Spray Test OP-Resistant

(7) Solvent: 78.0 parts by weight acetone 1.5 parts by weight dimethylformamide

(8) Emulsifier: alkylarylpolyglycol ether

(9) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvents and is diluted with water, containing an emulsifier concentration of 1000 ppm, to the desired concentration. To produce a suitable preparation of a spore suspension the spores are diluted with emulsifier containing water to the desired concentration. Further test concentrations are prepared by dilution with emulsifier containing water.

(10) French bean (Phaseolus vulgaris) leaf disks infected with all instars of the two spotted spidermite (Tetranychus urticae), are sprayed with a preparation of the active ingredient of the desired concentration.

(11) After the specified period of time, mortality in % is determined. 100% means all spider mites have been killed and 0% means none of the spider mites have been killed. The mortality values determined thus are recalculated using the Colby-formula (see above).

(12) According to the present application in this test e.g. the following combinations showed a synergistic effect in comparison to the single compounds:

(13) TABLE-US-00003 TABLE A-1 Tetranychus urticae - spray test Efficacy Concentration in % after Active Ingredient in g ai/ha 2 days Compound (Cpd) of formula (I) 0.5 0  0.125 0 Acequinocyl 1   0 obs.* cal.** Cpd of formula (I) + Acequinocyl 0.5 + 1   70 0 (1:2) according to the invention Compound (Cpd) of formula (IIa)  0.05 0 obs.* cal.** Cpd of formula (I) + Cpd of formula  0.5 + 0.05 70 0 (IIa) (10:1) according to the invention Diafenthiuron 0.5 0 obs.* cal.** Cpd of formula (I) + Diafenthiuron 0.5 + 0.5 100   0 (1:1) according to the invention Tebufenpyrad 0.5 0 obs.* cal.** Cpd of formula (I) + Tebufenpyrad 0.5 + 0.5 90 0 (1:1) according to the invention

(14) TABLE-US-00004 TABLE A-2 Tetranychus urticae - spray test Efficacy Concentration in % after Active Ingredient in g ai/ha 6 days Cpd of formula (I) 1.2 70  0.6 0 0.5 0 0.3 0  0.125 0 Acequinocyl 1   0    obs.* cal.** Cpd of formula (I) + Acequinocyl 0.5 + 1.sup.  70 0 (1:2) according to the invention Cpd of formula (IIa) 1.2 0  0.05 0   0.0125 0 obs.* cal.** Cpd of formula (I) + Cpd of formula 0.6 + 1.2 90 0 (IIa) (1:2) (10:1)  0.5 + 0.05 100  0 (10:1) according to the invention  0.125 + 0.0125 70 0 Bifenazate 1.8 0  0.25 0 obs.* cal.** Cpd of formula (I) + Bifenazate (1:3) 0.6 + 1.8 70 0 according to the invention Diafenthiuron 3   0 0.5 0 obs.* cal.** Cpd of formula (I) + Diafenthiuron 0.5 + 0.5 70 0 (1:1) (1:10) 0.3 + 3.sup.  90 0 according to the invention Fenazaquin 2.4 0 1.2 0 obs.* cal.** Cpd of formula (I) + Fenazaquin 0.6 + 2.4 90 0 (1:4) (1:4) according to the invention 0.3 + 1.2 90 0 Fenpyroximate 0.2 0 obs.* cal.** Cpd of formula (I) + Fenpyroximate 0.6 + 0.2 90 0 (3:1) according to the invention Methiocarb 12   0 6   0 obs.* cal.** Cpd of formula (I) + Methiocarb 0.6 + 12  90 0 (1:20) (1:20) according to the 0.3 + 6.sup.  70 0 invention Pyridaben 0.5 0 obs.* cal.** Cpd of formula (I) + Pyridaben (1:1) 0.5 + 0.5 90 0 according to the invention Requiem 18   0 obs.* cal.** Cpd of formula (I) + Requiem (1:30) 0.6 + 18  70 0 according to the invention Tebufenpyrad 0.5 0 obs.* cal.** Cpd of formula (I) + Tebufenpyrad 0.5 + 0.5 90 0 (1:1) according to the invention 0.125 + 0.125 70 0 *obs. = observed insecticidal efficacy, **cal. = efficacy calculated with Colby-formula

Example B

(15) Tetranychus urticae—Spray Test; OP-Resistant

(16) Solvent: 7 parts by weight of dimethylformamide

(17) Emulsifier: alkylaryl polyglycol ether

(18) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and is diluted with water, containing an emulsifier concentration of 1000ppm, to the desired concentration. Further test concentrations are prepared by dilution with emulsifier containing water.

(19) Bean plants (Phaseolus vulgaris) which are heavily infested with all stages of the two-spotted spider mite (Tetranychus urticae) are treated by being sprayed with the preparation of the active compound of the desired concentration.

(20) After the specified period of time mortality in % is determined. 100% means all the spider mites have been killed and 0% means none of the spider mites have been killed. The mortality values determined thus are recalculated using the Colby-formula (see above).

(21) According to the present application in this test e.g. the following combinations showed a synergistic effect in comparison to the single compounds:

(22) TABLE-US-00005 TABLE B-1 Tetranychus urticae - spray test Efficacy Concentration in % after Active Ingredient in ppm 3 days Cpd of formula (I) 0.4 0 Requiem 4 0 obs.* cal.** Cpd of formula (I) + Requiem 0.4 + 4 30 0 (1:10) according to the invention

(23) TABLE-US-00006 TABLE B-2 Tetranychus urticae - spray test Efficacy Concentration in % after Active Ingredient in ppm 4 days Cpd of formula (I) 0.8 25  0.4 0 MET 52 - Metarhizium anisopliae strain 8 0 F52 (5.5 x 109 spores/ml) 4 0 obs.* cal.** Cpd of formula (I) + MET 52 (1:10) 0.8 + 8 75 25 according to the invention 0.4 + 4 40  0

(24) TABLE-US-00007 TABLE B-3 Tetranychus urticae - spray test Efficacy Concentration in % after Active Ingredient in ppm 7 days Cpd of formula (I) 0.8 30 0.4 10 0.2  0 Cpd of formula (IIa) 0.4 55 0.2 10 obs.* cal.** Cpd of formula (I) + Cpd of formula   87.5 59.5 (IIa) (1:1) according to the invention 0.4 + 0.4 45 10   0.2 + 0.2 Bifenazate 2 65 obs.* cal.** Cpd of formula (I) + Bifenazate 0.4 + 2   95 68.5 (1:5) according to the invention Diafenthiuron 3.2 15 obs.* cal.** Cpd of formula (I) + Diafenthiuron (1:8) according to the invention 0.4 + 3.2 65 23.5 *obs. = observed insecticidal efficacy, **cal. = efficacy calculated with Colby-formula

Example C

(25) Meloidogvne incognita—Test

(26) Solvent: 125.0 parts by weight of acetone

(27) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water to the desired concentration.

(28) To produce a suitable preparation of a spore suspension the spores are diluted with water to the desired concentration.

(29) Vessels are filled with sand, a solution of the active ingredient, a suspension containing eggs and larvae of the southern root-knot nematode (Meloidogyne incognita) and salad seeds. The salad seeds germinate and the seedlings grow. Galls develop in the roots.

(30) After the specified period of time nematicidal activity is determined on the basis of the percentage of gall formation. 100% means no galls were found and 0% means the number of galls found on the roots of the treated plants was equal to that in untreated control plants.

(31) According to the present application in this test e.g. the following combinations showed a synergistic effect in comparison to the single compounds:

(32) TABLE-US-00008 TABLE C Meloidogyne incognita - test Efficacy Concentration in % after Active Ingredient in ppm 14 days Cpd of formula (I) 2   70  1   0 Fluazaindolizine  0.025 0 obs.* cal.** Cpd of formula (I) + Fluazaindolizine  1 + 0.025 90  0 (40:1) according to the invention Bacillus firmus 30   0 obs.* cal.** Cpd of formula (I) + Bacillus firmus 1 + 30  90  0 (1:30) according to the invention BioAct WG 60   0 obs.* cal.** Cpd of formula (I) + BioAct WG 2 + 60  100  70 (1:30) according to the invention Cpd of formula (IIb) (═N-[1-(2,6- 1.5 0 difluorophenyl)-1 H-pyrazol-3-yl]-2- (trifluoromethyl)benzamide) obs.* cal.** Cpd of formula (I) + Cpd of formula 1 + 1.5 70 0 (IIb) (1:1.5) according to the invention Fluensulfone 0.2 0 0.1 0 obs.* cal.** Cpd of formula (I) + Fluensulfone 2 + 0.2 100  70  (10:1) according to the invention 1 + 0.1 90  0

Example D

(33) Meloidogyne incognita—Test

(34) Solvent: 7 parts by weight of dimethylformamide

(35) Emulsifier: 2.5 parts by weight of alkylarylpolyglycolether

(36) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier and is diluted with water to the desired concentration. To produce a suitable preparation of a spore suspension the spores are diluted with emulsifier containing water to the desired concentration. In the calculation of the concentration the soil volume has to be included. Care has to be taken that the emulsifier concentration in the soil does not exceed 20 ppm. Further test concentrations are prepared by dilution with water.

(37) The compound solution is poured into pots filled with soil (loamy sand). A suspension containing eggs and larvae of the southern root-knot nematode (Meloidogyne incognita) is added, salad seeds are spread on the soil surface and covered with quartz sand. The salad seeds germinate and the seedlings grow. Galls develop on the roots.

(38) After the specified period of time the nematicidal activity is determined on the basis of the percentage of gall formation. 100% means no galls were found; 0% means the number of galls found on the roots of the treated plants was equal to that in untreated control plants. The activity determined thus is recalculated using the Colby-formula (see above).

(39) According to the present application in this test e.g. the following combinations showed a synergistic effect in comparison to the single compounds:

(40) TABLE-US-00009 TABLE D Meloidogyne incognita - test Efficacy Concentration in % after Active Ingredient in ppm 20 days Cpd of formula (I) 20 15  10 0 Fluopyram 0.08 0 0.04 0 obs.* cal.** Cpd of formula (I) + Fluopyram 250:1  20 + 0.08 90 15  according to the invention  10 + 0.04 65 0 Fluensulfone 0.4 0 obs.* cal.** Cpd of formula (I) + Fluensulfone 50:1 20 + 0.4 90 15 according to the invention Fluazaindolizine 0.4 40  0.2 0 obs.* cal.** Cpd of formula (I) + Fluazaindolizine 20 + 0.4 100  49  50:1 according to the invention 10 + 0.2 65 0 Cpd of formula (IIb) 0.4 0 obs.* cal.** Cpd of formula (I) + Cpd of formula 20 + 0.4 100  15  (IIb) 50:1 according to the invention Tioxazafen 1.25 0 obs.* cal.** Cpd of formula (I) + Tioxazafen 8:1 10 + 1.25 75 0 according to the invention *obs. = observed insecticidal efficacy, **cal. = efficacy calculated with Colby-formula