INSECTICIDAL AND NEMATOCIDAL ACTIVE INGREDIENT COMBINATIONS

Abstract

The present invention relates to active ingredient combinations which comprise a known compound of the formula (I)

##STR00001##

on the one hand and one or more other active pesticidal ingredients on the other and which are suitable for controlling animal and microbial pests.

Claims

1. Active ingredient combination comprising a compound of the formula (I) ##STR00012## in which A is A-1.0 or A-2.0 in which the dotted line represents the bond to the N atom of Q; Q is Q-1.0 or Q-2.0 in which the nitrogen is attached to ring A and the arrow in each case represents the bond to the NHCO moiety; W represents a radical from the group consisting of W1 to W11 ##STR00013## ##STR00014## and one or more than one compound/biological control agent selected from the mixing partners identified in the table below: TABLE-US-00019 No. Mixing partner 1. Imidacloprid 2. Clothianidin 3. Thiacloprid 4. Sulfoxaflor 5. Flupyradifurone 4-{[(6-chloropyrid-3- yl)methyl](2,2- difluoroethyl)amino}furan- 2(5H)-one 6. Carbofuran 7. Thiodicarb 8. Oxamyl 9. Cadusafos 10. Fosthiazate 11. Imicyafos 12. Tefluthrin 13. Chlorantraniliprole (FCH 1557) 14. Cyantraniliprole (FCH 1706) 15. Flubendiamide 16. 1-(3-chloropyridin-2-yl)-N-[4- cyano-2-methyl-6- (methylcarbamoyl)phenyl]-3- {[5-(trifluoromethyl)-2H- tetrazol-2-yl]methyl}-1H- pyrazole-5-carboxamide 17. Fipronil 18. Ethiprole 19. Abamectin 20. Emamectin-benzoate 21. Fluensulfone 22. Dimethyl-disulfide 23. 1-{2-fluoro-4-methyl-5- [(2,2,2- trifluoroethyl)sulfinyl]phenyl}- 3-(trifluoromethyl)-1H-1,2,4- triazol-5-amine 24. Triflumezopyrim 25. Iprodione 26. Fluopyram 27. 8-chloro-N-[(2-chloro-5- methoxyphenyl)sulfonyl]-6- (trifluoromethyl)imidazo[1,2- a]pyridine-2-carboxamide 28. Tioxazafen 29. Pasteuria penetrans 30. Pasteuria nishizawae 31. Pasteuria usage 32. Pasteuria spp. Pr3 33. Myrothecium verrucaria 34. Flavobacterium MBI-302 35. Serenade soil/DPZ 36. Paecilomyces lilacinus 37. Bacillus firmus I-1582 38. Azadirachtin

2. Active ingredient combination according to claim 1, where in the formula (I) A is A-1.0, Q is Q-1.0 and W is W1.

3. Active ingredient combination according to claim 1, where in the formula (I) A is A-2.0, Q is Q-1.0 and W is W1.

4. Active ingredient combination according to claim 1, where in the formula (I) A is A-1.0, Q is Q-2.0 and W is W1.

5. Active ingredient combinations according to claim 1, in which besides the compound of the formula (I) there is only one (1) compound/biological control agent selected from the compounds identified in the table.

6. An active ingredient combination according to claim 1 for controlling animal pests.

7. An active ingredient combination according to claim 1 for treating seed, soil and plants.

8. An active ingredient combination according to claim 1 adapted for transgenic plants.

9. Composition containing an active ingredient combination according to claim 1 and one or more than one extender and/or one or more than one surfactant.

10. Method for producing a crop protection composition, comprising mixing an active ingredient combination according to claim 1 with one or more than one extender and/or one or more than one surfactant.

Description

PREPARATION EXAMPLES

Preparation of N-[1-(2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (Compound (Ia))

[0105] ##STR00008##

Step 1: 1-(2,6-Difluorophenyl)-4,5-dihydro-1H-pyrazole-3-amine (Intermediate (Ia-1))

[0106] 2,6-Difluorophenylhydrazine hydrochloride (2.00 g) was initially charged in ethanol (20 ml), sodium ethoxide (21% in ethanol, 3.02 g) was slowly added dropwise at room temperature, the mixture was stirred for 10 min, acrylonitrile (0.80 ml) was added and the mixture was heated under reflux overnight. The reaction mixture was then concentrated under reduced pressure, taken up in dichloromethane, washed with water, dried over sodium sulphate and concentrated to dryness under reduced pressure. What remained was 1.40 g of the title compound which was used without further purification for the next step.

Step 2: N-[1-(2,6-Difluorophenyl)-4,5-dihydro-1H-pyrazol-3-yl]acetamide (Intermediate (Ia-2))

[0107] With ice cooling, 1-(2,6-difluorophenyl)-4,5-dihydro-1H-pyrazole-3-amine (Ia-1) (1.40 g from previous step) was dissolved in acetic anhydride (6 ml) and stirred at room temperature overnight. The mixture was then diluted with ethyl acetate, washed with water, dried over sodium sulphate and concentrated to dryness under reduced pressure. The residue was purified by column chromatography on silica gel using the mobile phase cyclohexane/ethyl acetate (gradient=2 h from 100% cyclohexane to 100% ethyl acetate). This gave 537 mg of the title compound. HPLC-MS: log P=1.46; mass (m/z): 240.0 (M+H)+; 1H-NMR (DMSO-D6) 1.99 (s, 3H), 3.26 (t, 2H), 3.65 (t, 2H), 7.04-7.10 (m, 2H), 7.11-7.18 (m, 1H), 10.59 (br. s, 1H).

Step 3: N-[1-(2,6-Difluorophenyl)-1H-pyrazol-3-yl]acetamide (Intermediate (Ia-3))

[0108] N-[1-(2,6-Difluorophenyl)-4,5-dihydro-1H-pyrazol-3-yl]acetamide (Ia-2) (200 mg) was initially charged in 1,4-dioxane (1 ml), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (209 mg) was added and the mixture was stirred at room temperature for 30 min. The reaction mixture was filtered and the filtrate was concentrated to dryness under reduced pressure. The residue was purified by column chromatography on silica gel using the mobile phase cyclohexane/ethyl acetate (gradient=2 h from 100% cyclohexane to 100% ethyl acetate). This gave 140 mg of the title compound.

[0109] HPLC-MS: log P=1.33; mass (m/z): 238.0 (M+H)+; 1H-NMR (CD3CN) 2.07 (s, 3H), 6.84 (d, 1H), 7.14-7.20 (m, 2H), 7.47-7.53 (m, 1H), 7.65-7.66 (m, 1H), 8.76 (br. s, 1H).

Step 4: 1-(2,6-Difluorophenyl)-1H-pyrazole-3-amine (Intermediate (Ia-4))

[0110] N-[1-(2,6-Difluorophenyl)-1H-pyrazol-3-yl]acetamide (Ia-3) (50 mg) was initially charged in water (1 ml), concentrated hydrochloric acid (0.07 ml) was added and the mixture was heated under reflux for 8 h. The reaction mixture was then made alkaline with concentrated aqueous sodium hydroxide solution and extracted with dichloromethane. The organic phase was concentrated to dryness under reduced pressure. This gave 25 mg of the title compound.

[0111] HPLC-MS: log P=1.13; mass (m/z): 196.1 (M+H)+; 1H-NMR (CD3CN) 4.12 (br. s, 2H), 5.83 (d, 1H), 7.09-7.16 (m, 2H), 7.37-7.44 (m, 1H), 7.46-7.47 (m, 1H).

Step 5: N-[1-(2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (Compound (Ia))

[0112] 1-(2,6-Difluorophenyl)-1H-pyrazole-3-amine (Ia-4) (1 g) was initially charged in dichloromethane (10 ml). The reaction mixture was cooled down to 0 C.; 2.142 mL of triethylamine were added. Then 2-(trifluoromethyl)benzoyl chloride (1.175 g) was added dropwise with a temperature between 0 C. and 5 C. The reaction mixture was stirred overnight at room temperature. Some dichloromethane and water were then added. The organic phase was separated, dried and evaporated. The residue obtained was purified by column chromatography on silica gel using a gradient of cyclohexane/ethyl acetate. This gave 1.2 g of the title compound.

[0113] HPLC-MS: log P=2.68; mass (m/z): 368.1 (M+H)+; 1H-NMR [CD3CN] 6.99 (d, 1H), 7.16-7.22 (m, 2H), 7.47-7.54 (m, 1H), 7.65-7.76 (m, 4H), 7.80-7.82 (m, 1H), 9.30 (br. s, 1H).

Preparation of N-[1-(3,5-difluoropyridin-2-yl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (Compound (Ib))

[0114] ##STR00009##

Step 1: 1-(3,5-Difluoropyridin-2-yl)-1H-pyrazole-3-amine (Intermediate (Ib-1)

[0115] 1H-Pyrazole-3-amine (1.80 g) was initially charged in acetonitrile (50 ml), 2,3,5-trifluoropyridine (2.88 g) and potassium carbonate (5.99 g) were added and the mixture was heated under reflux overnight. The reaction mixture was then concentrated under reduced pressure, taken up in dichloromethane, washed with water, dried over sodium sulphate and concentrated to dryness under reduced pressure. The residue was purified by column chromatography on silica gel using the mobile phase cyclohexane/ethyl acetate (gradient=2 h from 100% cyclohexane to 100% ethyl acetate). This gave 610 mg of the title compound.

[0116] HPLC-MS: log P=0.81; mass (m/z): 197.1 (M+H)+; 1H-NMR (CD3CN) 4.27 (br. s, 2H), 5.88 (d, 1H), 7.56-7.62 (m, 1H), 7.99-8.00 (m, 1H), 8.17-8.18 (m, 1H).

Step 2: N-[1-(3,5-difluoropyridin-2-yl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (Compound (Ib))

[0117] 1-(3,5-Difluoropyridin-2-yl)-1H-pyrazole-3-amine (Ib-1) (300 mg) was initially charged in dichloromethane (2 ml). The reaction mixture was cooled down to 0 C.; 0.640 ml of triethylamine were added. Then 2-(trifluoromethyl)benzoyl chloride (0.256 ml) was added dropwise with a temperature between 0 C. and 5 C. The reaction mixture was stirred overnight at room temperature. Some dichloromethane and water were then added. The organic phase was separated, dried and evaporated. The residue obtained was purified by column chromatography on silica gel using a gradient of cyclohexane/ethyl acetate. This gave 506 mg of the title compound.

[0118] HPLC-MS: log P=2.48; mass (m/z): 369.1 (M+H)+; 1H-NMR [CD3CN] 7.03 (d, 1H), 7.62-7.70 (m, 4H), 7.77-7.79 (m, 1H), 8.20 (d, 1H), 8.25 (d, 1H), 9.47 (br. s, 1H).

Preparation of N-[2-(2,6-Difluorophenyl)-2H-1,2,3-triazol-4-yl]-2-(trifluoromethyl)benzamide (Compound (Ic))

[0119] ##STR00010## ##STR00011##

Step 1: 2-[2-(2,6-Difluorophenyl)hydrazinylidene]propanal oxime (Intermediate (Ic-1))

[0120] 0.1 mol of 2,6-difluorophenylhydrazine and 0.12 mol of isonitrosoacetone were heated under reflux in ethanol for 3 h. After cooling to room temperature, the precipitated solid was filtered off, washed with ethanol and dried. This gave the title compound (75% of theory)

Step 2: 2-(2,6-Difluorophenyl)-4-methyl-2H-1,2,3-triazole (Intermediate (Ic-2))

[0121] A solution of 0.1 mol of the 2-[2-(2,6-difluorophenyl)hydrazinylidene]propanal oxime (Ic-1) in acetic anhydride was heated slowly to 120 C. and stirred at this temperature for 2 h. Excess of acetic anhydride was removed on a rotary evaporator. The title compound was obtained (65% of theory) and was used without further purification.

Step 3: 2-(2,6-Difluorophenyl)-2H-1,2,3-triazole-4-carboxylic acid (Intermediate (Ic-3))

[0122] 0.2 mol of sodium dichromate was added to a well-stirred solution of 0.1 mol of 2-(2,6-difluorophenyl)-4-methyl-2H-1,2,3-triazole (Ic-2) in 66% sulphuric acid. Each individual portion of dichromate was added only after the yellow-orange colour of the Cr6+ in the flask had disappeared. Moreover, the portions were added such that the temperature in the flask remained at about 80-90 C. The mixture was then heated for 1 h. After cooling, the mixture was poured into about the same amount of ice and allowed to stand overnight. The precipitated acid (Ic-3) was filtered off, washed with water and dried. This gave the title compound (50% of theory).

Step 4: Methyl 2-(2,6-difluorophenyl)-2H-1,2,3-triazole-4-carboxylate (Intermediate (Ic-4))

[0123] Hydrogen chloride was bubbled for 2 h through a boiling solution of 2-(2,6-difluorophenyl)-2H-1,2,3-triazole-4-carboxylic acid (Ic-3) in methanol. After cooling, white crystals of the title compound were filtered off (85% of theory).

Step 5: 2-(2,6-Difluorophenyl)-2H-1,2,3-triazole-4-carbohydrazide (Intermediate (Ic-5))

[0124] Methyl 2-(2,6-difluorophenyl)-2H-1,2,3-triazole-4-carboxylate (Ic-4) was boiled with an excess of 1.5 eq. of hydrazine hydrate in ethanol for 4 h. After cooling, the crystals of the hydrazide (Ic-5) were boiled with water and dried. This gave the title compound (90% of theory).

Step 6: 2-(2,6-Difluorophenyl)-2H-1,2,3-triazole-4-carbonyl azide (Intermediate (Ic-6))

[0125] An aqueous solution of sodium nitrite was added to a suspension of 2-(2,6-Difluorophenyl)-2H-1,2,3-triazole-4-carbohydrazide (Ic-5) in 20% aqueous hydrochloric acid. After further stirring at 10 C., the crystals of the acyl azide (Ic-6) were filtered off, washed with water and dried at room temperature under reduced pressure. This gave the title compound (75% of theory).

Step 7: 2-(2,6-Difluorophenyl)-2H-1,2,3-triazole-4-carbonyl isocyanate (Intermediate (Ic-7))

[0126] 2-(2,6-Difluorophenyl)-2H-1,2,3-triazole-4-carbonyl azide (Ic-6) dried was boiled in toluene until the evolution of gas had ended (about 2 h). The toluene was then removed on a rotary evaporator and the viscous residue of the isocyanate (Ic-7) was directly ready for the next step without further purification. This gave the title compound (90% of theory).

Step 8: 2-(2,6-Difluorophenyl)-2H-1,2,3-triazole-4-amine (Intermediate (Ic-8))

[0127] 2-(2,6-Difluorophenyl)-2H-1,2,3-triazole-4-carbonyl isocyanate (Ic-7) was hydrolyzed by 30 min of boiling in hydrochloric acid. Residual volatile substances were removed on a rotary evaporator, and the residue was treated with sodium carbonate solution. The precipitated crystals were filtered off, washed with water and recrystallized from hexane. This gave the title compound (70% of theory).

[0128] HPLC-MS: log P=1.16; mass (m/z): 197.0 (M+H)+; 1H-NMR (CD3CN) 5.46 (b, 2H), 7.33-7.38 (m, 3H), 7.56-7.64 (m, 1H).

Step 9: N-[2-(2,6-Difluorophenyl)-2H-1,2,3-triazol-4-yl]-2-(trifluoromethyl)benzamide (Compound Ic)

[0129] 2,2-(2,6-difluorophenyl)-2H-1,2,3-triazole-4-amine (Ic-8) (150 mg) was reacted with 2-(trifluoromethyl)benzoyl chloride (160 mg) and triethylamine (0.21 ml) in 3.9 ml of dichloromethane. Purification by column chromatography and preparative HPLC gave 143 mg of the title compound. HPLC-MS: log P=2.80; mass (m/z): 369.1 (M+H)+; 1H-NMR (CD3CN) 7.45-7.49 (m, 2H), 7.70-7.77 (m, 4H), 7.78-7.88 (m, 1H), 8.45 (s, 1H), 11.83 (s, 1H).

USE EXAMPLES

Formula for the Efficacy of the Combination of Two Compounds

[0130] 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):

[0131] If [0132] X is the efficacy expressed in % mortality of the untreated control for test compound A at a concentration of m ppm or m g/ha, [0133] Y is the efficacy expressed in % mortality of the untreated control for test compound B at a concentration of n ppm or n g/ha, [0134] 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

[00001]$E=X+Y-\frac{XY}{100}$ [0135] 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.

SchneiderOrelli: Formula to Calculate Corrected Efficacy % in Pesticide Trials

[0136] [00002]$\mathrm{Corrected}.Math..Math.\%=\left(\frac{\mathrm{Mortality}.Math..Math..Math.\%.Math..Math.\mathrm{in}.Math..Math.\mathrm{treated}.Math..Math.\mathrm{plot}-\text{Mortality}.Math..Math.\%.Math..Math.\mathrm{in}.Math..Math.\mathrm{control}.Math..Math.\mathrm{plot}}{100-M.Math.\mathrm{ortality}.Math..Math.\%.Math..Math.\mathrm{in}.Math..Math.\mathrm{control}.Math..Math.\mathrm{plot}}\right)100$

Example A

Meloidogyne incognitaTest

[0137]

TABLE-US-00009 Solvent: 125.0 parts by weight of acetone

[0138] 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. To produce a suitable preparation of a spore suspension the spores are diluted with water to the desired concentration.

[0139] 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.

[0140] After the specified period 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.

[0141] According to the present application in this test e.g. the following combinations showed a synergistic effect in comparison to the single compounds:

TABLE-US-00010 TABLE A Meloidogyne incognita - test Concentration Efficacy Active Ingredient in ppm in % after 14.sup.d Compound (Ia) 10 0 5 0 1 0 Compound (Ic) 10 70 5 0 1 0 0.25 0 Abamectin 0.08 0 0.02 0 obs.* cal.** Compound (Ia) + Abamectin 1 + 0.08 90 0 (12.5:1) according to the invention obs.* cal.** Compound (Ic) + Abamectin 1 + 0.08 90 0 (12.5:1) 0.25 + 0.02 90 0 according to the invention Azadirachtin 16 0 obs.* cal.** Compound (Ia) + Azadirachtin 1 + 16 90 0 (1:16) according to the invention obs.* cal.** Compound (Ic) + Azadirachtin 1 + 16 90 0 (1:16) according to the invention Cadusafos 100 0 50 0 obs.* cal.** Compound (Ia) + Cadusafos 10 + 100 90 0 (1:10) 5 + 50 90 0 according to the invention obs.* cal.** Compound (Ic) + Cadusafos 5 + 50 70 0 (1:10) according to the invention Carbofuran 100 0 50 0 obs.* cal.** Compound (Ia) + Carbofuran 10 + 100 90 0 (1:10) according to the invention obs.* cal.** Compound (Ic) + Carbofuran 5 + 50 70 0 (1:10) according to the invention Iprodione 100 0 50 0 obs.* cal.** Compound (Ia) + Iprodione 10 + 100 90 0 (1:10) 5 + 50 90 0 according to the invention obs.* cal.** Compound (Ic) + Iprodione 10 + 100 100 70 (1:10) 5 + 50 70 0 according to the invention Thiodicarb 50 0 obs.* cal.** Compound (Ia) + Thiodicarb 5 + 50 90 0 (1:10) according to the invention obs.* cal.** Compound (Ic) + Thiodicarb 5 + 50 90 0 (1:10) according to the invention Serenade soil 200 0 obs.* cal.** Compound (Ia) + Serenade soil 10 + 200 90 0 (1:20) according to the invention *obs. = observed insecticidal efficacy, **cal. = efficacy calculated with Colby-formula

Example B

Spodoptera frugiperdaDrench Test

[0142] Solvent: 7 parts by weight of dimethylformamide

[0143] Emulsifier: 2 parts by weight of alkylaryl poly glycol ether

[0144] 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. 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 40 ppm. Further test concentrations are prepared by dilution with water.

[0145] Corn plant leaves (Zea mays)) in pots filled with soil, are treated by being drenched with the preparation of the active compound of the desired concentration and are infested with caterpillars of the fall army worm (Spodoptera frugiperda).

[0146] After the specified period of time mortality in % is determined and corrected according to Schneider-Orelli's formula (see sheet 1). 100% means all the caterpillars have been killed and 0% means none of the caterpillars have been killed. The mortality values determined thus are recalculated using the Colby-formula (see sheet 1).

[0147] According to the present application in this test e.g. the following combinations showed a synergistic effect in comparison to the single compounds:

TABLE-US-00011 TABLE B-1 Spodoptera frugiperda - drench test Concentration Efficacy Active Ingredient in ppm in % after 4.sup.d Compound (Ia) 200 0 Compound (Ic) 200 0 Compound (Ib) 200 0 Clothianidin 10 0 obs.* cal.** Compound (Ic) + Clothianidin 200 + 10 66 0 (20:1) according to the invention obs.* cal.** Compound (Ib) + Clothianidin 200 + 10 89 0 (20:1) according to the invention Imidacloprid 50 22 obs.* cal.** Compound (Ia) + Imidacloprid 200 + 50 55 22 (4:1) according to the invention obs.* cal.** Compound (Ic) + Imidacloprid 200 + 50 55 22 (4:1) according to the invention

TABLE-US-00012 TABLE B-2 Spodoptera frugiperda - drench test Concentration Efficacy Active Ingredient in ppm in % after 6.sup.d Compound (Ia) 200 0 Compound (Ic) 200 0 Compound (Ib) 200 0 Imidacloprid 50 12 10 0 obs.* cal.** Compound (Ia) + Imidacloprid 200 + 50 49 12 (4:1) according to the invention obs.* cal.** Compound (Ic) + Imidacloprid 200 + 50 100 12 (4:1) 200 + 10 49 0 (20:1) according to the invention obs.* cal.** Compound (Ib) + Imidacloprid 200 + 50 88 12 (4:1) 200 + 10 49 0 (20:1) according to the invention Clothianidin 10 37 2 0 obs.* cal.** Compound (Ia) + Clothianidin 200 + 10 88 37 (20:1) according to the invention obs.* cal.** Compound (Ic) + Clothianidin 200 + 10 74 37 (20:1) according to the invention obs.* cal.** Compound (Ib) + Clothianidin 200 + 10 88 37 (20:1) 200 + 2 37 0 (100:1) according to the invention

TABLE-US-00013 TABLE B-3 Spodoptera frugiperda - drench test Concentra- tion Efficacy Active Ingredient in ppm in % after 14.sup.d Compound (Ia) 40 0 0.2 0 Compound (Ic) 0.8 0 0.2 0 Compound (Ib) 40 0 Chlorantraniliprole 0.04 66.5 obs.* cal.** Compound (Ia) + Chlorantraniliprole 0.2 + 0.04 100 66.5 (5:1) according to the invention obs.* cal.** Compound (Ic) + Chlorantraniliprole 0.2 + 0.04 100 66.5 (5:1) according to the invention Cyantraniliprole 0.08 16.5 obs.* cal.** Compound (Ic) + Cyantraniliprole 0.8 + 0.08 66 16.5 (10:1) according to the invention Flubendiamide 8 66 4 33 obs.* cal.** Compound (Ia) + Flubendiamide 40 + 4 83 33 (10:1) according to the invention obs.* cal.** Compound (Ib) + Flubendiamide 40 + 8 100 66 (5:1) 40 + 4 100 33 (10:1) according to the invention *obs. = observed insecticidal efficacy, **cal. = efficacy calculated with Colby-formula

Example C

Meloidogyne incognitaDrench Test

[0148]

TABLE-US-00014 Solvent: 7 parts by weight of dimethylformamide Emulsifier: 2.5 parts by weight of alkylarylpolyglycolether

[0149] 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. 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.

[0150] 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.

[0151] 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 sheet 1).

[0152] According to the present application in this test e.g. the following combinations showed a synergistic effect in comparison to the single compounds:

TABLE-US-00015 TABLE C Meloidogyne incognita - drench test Concentration Efficacy Active Ingredient in ppm in % after 21.sup.d Compound (Ia) 0.75 0 Compound (Ib) 0.75 55 Fluopyram 0.15 0 obs.* cal.** Compound (Ia) + Fluopyram 0.75 + 0.15 97 0 (5:1) according to the invention obs.* cal.** Compound (Ib) + Fluopyram 0.75 + 0.15 95 55 (5:1) according to the invention *obs. = observed insecticidal efficacy, **cal. = efficacy calculated with Colby-formula

Example D

[0153] Myzus persicaeDrench Test

[0154] Solvent: 7 parts by weight of dimethylformamide

[0155] Emulsifier: 2 parts by weight of alkylaryl poly glycol ether

[0156] 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. 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 40 ppm. Further test concentrations are prepared by dilution with water.

[0157] Cabbage plants (Brassica oleracea)) in pots filled with soil, which are heavily infested with the green peach aphid (Myzus persicae), are treated by being drenched with the preparation of the active compound of the desired concentration.

[0158] After the specified period of time mortality in % is determined. 100% means all the aphids have been killed and 0% means none of the aphids have been killed. The mortality values determined thus are recalculated using the Colby-formula (see sheet 1).

[0159] According to the present application in this test e.g. the following combinations showed a synergistic effect in comparison to the single compounds:

TABLE-US-00016 TABLE D-1 Myzus persicae - drench test Concentra- tion Efficacy Active Ingredient in ppm in % after 7.sup.d Compound (Ia) 20 0 2 0 Compound (Ic) 20 0 2 0 Compound (Ib) 20 0 2 0 N-[1-[(6-chloro-3-pyridinyl)methyl]- 0.1 30 2(1H)-pyridinylidene]-2,2,2-trifluoro- acetamide obs.* cal.** Compound (Ib) + N-[1-[(6-chloro-3- 2 + 0.1 70 30 pyridinyl)methyl]-2(1H)- pyridinylidene]-2,2,2-trifluoro- acetamide (20:1) according to the invention 1-(3-chloropyridin-2-yl)-N-[4-cyano- 0.25 0 2-methyl-6- (methylcarbamoyl)phenyl]-3-{[5- (trifluoromethyl)-2H-tetrazol-2- yl]methyl}-1H-pyrazole-5- carboxamide obs.* cal.** Compound (Ia) + 1-(3-chloropyridin- 2 + 0.25 60 0 2-yl)-N-[4-cyano-2-methyl-6- (methylcarbamoyl)phenyl]-3-{[5- (trifluoromethyl)-2H-tetrazol-2- yl]methyl}-1H-pyrazole-5- carboxamide (8:1) according to the invention obs.* cal.** Compound (Ic) + 1-(3-chloropyridin- 2 + 0.25 85 0 2-yl)-N-[4-cyano-2-methyl-6- (methylcarbamoyl)phenyl]-3-{[5- (trifluoromethyl)-2H-tetrazol-2- yl]methyl}-1H-pyrazole-5- carboxamide (8:1) according to the invention Chlorantraniliprole 1.6 20 0.8 10 obs.* cal.** Compound (Ia) + Chlorantraniliprole 2 + 1.6 50 20 (1.25:1) according to the invention obs.* cal.** Compound (Ic) + Chlorantraniliprole 2 + 1.6 60 20 (1.25:1) 2 + 0.8 45 10 (2.5:1) according to the invention obs.* cal.** Compound (Ib) + Chlorantraniliprole 2 + 1.6 95 20 (1.25:1) 2 + 0.8 60 10 (2.5:1) according to the invention Cyantraniliprole 0.1 20 obs.* cal.** Compound (Ic) + Cyantraniliprole 2 + 0.1 75 20 (20:1) according to the invention obs.* cal.** Compound (Ib) + Cyantraniliprole 2 + 0.1 55 20 (20:1) according to the invention Fipronil 10 40 5 15 obs.* cal.** Compound (Ia) + Fipronil 20 + 10 80 40 (2:1) 20 + 5 80 15 (4:1) according to the invention obs.* cal.** Compound (Ic) + Fipronil 20 + 10 75 40 (2:1) 20 + 5 70 15 (4:1) according to the invention obs.* cal.** Compound (Ib) + Fipronil 20 + 10 80 40 (2:1) 20 + 5 80 15 (4:1) according to the invention

TABLE-US-00017 TABLE D-2 Myzus persicae - drench test Concentra- tion Efficacy Active Ingredient in ppm in % after 10.sup.d Compound (Ia) 20 0 2 0 Compound (Ic) 2 0 Compound (Ib) 2 0 N-[1-[(6-chloro-3-pyridinyl)methyl]- 0.1 20 2(1H)-pyridinylidene]-2,2,2-trifluoro- acetamide obs.* cal.** Compound (Ib) + N-[1-[(6-chloro-3- 2 + 0.1 50 20 pyridinyl)methyl]-2(1H)- pyridinylidene]-2,2,2-trifluoro- acetamide (20:1) according to the invention 1-(3-chloropyridin-2-yl)-N-[4-cyano- 0.25 0 2-methyl-6- (methylcarbamoyl)phenyl]-3-{[5- (trifluoromethyl)-2H-tetrazol-2- yl]methyl}-1H-pyrazole-5- carboxamide obs.* cal.** Compound (Ia) + 1-(3-chloropyridin- 2 + 0.25 90 0 2-yl)-N-[4-cyano-2-methyl-6- (methylcarbamoyl)phenyl]-3-{[5- (trifluoromethyl)-2H-tetrazol-2- yl]methyl}-1H-pyrazole-5- carboxamide (8:1) according to the invention obs.* cal.** Compound (Ic) + 1-(3- 2 + 0.25 90 0 chloropyridin-2-yl)-N-[4-cyano-2- methyl-6-(methylcarbamoyl)phenyl]- 3-{[5-(trifluoromethyl)-2H-tetrazol-2- yl]methyl}-1H-pyrazole-5- carboxamide (8:1) according to the invention obs.* cal.** Compound (Ib) + 1-(3-chloropyridin- 2 + 0.25 30 0 2-yl)-N-[4-cyano-2-methyl-6- (methylcarbamoyl)phenyl]-3-{[5- (trifluoromethyl)-2H-tetrazol-2- yl]methyl}-1H-pyrazole-5- carboxamide (8:1) according to the invention Chlorantraniliprole 0.4 0 obs.* cal.** Compound (Ic) + 2 + 0.4 40 0 Chlorantraniliprole (5:1) according to the invention obs.* cal.** Compound (Ib) + Chlorantraniliprole 2 + 0.4 45 0 (5:1) according to the invention Cyantraniliprole 0.1 10 obs.* cal.** Compound (Ia) + Cyantraniliprole 2 + 0.1 55 10 (1.25:1) according to the invention obs.* cal.** Compound (Ic) + Cyantraniliprole 2 + 0.1 70 10 (20:1) according to the invention obs.* cal.** Compound (Ib) + Cyantraniliprole 2 + 0.1 40 10 (20:1) according to the invention Fipronil 10 55 5 50 obs.* cal.** Compound (Ia) + Fipronil 20 + 10 90 55 (2:1) 20 + 5 90 50 (4:1) according to the invention *obs. = observed insecticidal efficacy, **cal. = efficacy calculated with Colby-formula

Example E

Tetranychus urticaeDrench Test; OP-Resistant

[0160] Solvent: 7 parts by weight of dimethylformamide

[0161] Emulsifier: 2 parts by weight of alkylaryl poly glycol ether

[0162] 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. 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 40 ppm. Further test concentrations are prepared by dilution with water.

[0163] Bean plants (Phaseolus vulgaris) in pots filled with soil, which are heavily infested with all stages of the two-spotted spider mite (Tetranychus urticae), are treated by being drenched with the preparation of the active compound of the desired concentration.

[0164] 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 sheet 1).

[0165] According to the present application in this test e.g. the following combinations showed a synergistic effect in comparison to the single compounds:

TABLE-US-00018 TABLE E Tetranychus urticae - drench test Concentration Efficacy Active Ingredient in ppm in % after 15.sup.d Compound (Ia) 25 10 Compound (Ic) 25 0 Compound (Ib) 25 0 Emamectin-benzoate 2 10 obs.* cal.** Compound (Ia) + Emamectin- 25 + 2 75 19 benzoate (12.5:1) according to the invention obs.* cal.** Compound (Ic) + Emamectin- 25 + 2 85 10 benzoate (12.5:1) according to the invention obs.* cal.** Compound (Ib) + Emamectin- 25 + 2 55 10 benzoate (12.5:1) according to the invention *obs. = observed insecticidal efficacy, **cal. = efficacy calculated with Colby-formula